High-pressure phase equilibria in a garnet lherzolite,with special reference to Mg²⁺Fe²⁺ partitioning among constituent minerals     

M. Akaogi  S. Akimoto 《Physics of the Earth and Planetary Interiors》1979,19(1):31-51

Phase equilibria in a natural garnet lherzolite nodule (PHN 1611) from Lesotho kimberlite and its chemical analogue have been studied in the pressure range 45–205 kbar and in the temperature range 1050–1200°C. Partition of elements, particularly Mg²⁺Fe²⁺, among coexisting minerals at varying pressures has also been examined. High-pressure transformations of olivine(α) to spinel(γ) through modified spinel(β) were confirmed in the garnet lherzolite. The transformation behavior is quite consistent with the information previously accumulated for the simple system Mg₂SiO₄Fe₂SiO₄. At pressures of 50–150 kbar, a continuous increase in the solid solubility of the pyroxene component in garnet was demonstrated in the lherzolite system by means of microprobe analyses. At 45–75 kbar and 1200°C, the Fe²⁺/(Mg + Fe²⁺) value becomes greater in the ascending order orthopyroxene, Ca-rich clinopyroxene, olivine and garnet. At 144–146 kbar and 1200°C, garnet exhibits the highest Fe²⁺/(Mg + Fe²⁺) value; modified spinel(β) and Ca-poor clinopyroxene follow it. When the modified spinel(β)-spinel(γ) transformation occurred, a higher concentration of Fe²⁺ was found in spinel(γ) rather than in garnet. As a result of the change in the Mg²⁺Fe²⁺ partition relation among coexisting minerals, an increase of about 1% in the Fe₂SiO₄ component in (Mg,Fe)₂SiO₄ modified spinel and spinel was observed compared with olivine.These experimental results strongly suggest that the olivine(α)-modified spinel(β) transformation is responsible for the seismic discontinuity at depths of 380–410 km in the mantle. They also support the idea that the minor seismic discontinuity around 520 km is due to the superposition effect of two types of phase transformation, i.e. the modified spinel(β)-spinel(γ) transformation and the pyroxene-garnet transformation. Mineral assemblages in the upper mantle and the upper half of the transition zone are given as a function of depth for the following regions: 100–150, 150–380, 380–410, 410–500, 500–600 and 600–650 km.  相似文献   

The location of Fe³⁺ ions in forsterite (Mg₂SiO₄)     

S. Zeira  S.S. Hafner 《Earth and Planetary Science Letters》1974,21(2):201-208

The electron spin resonance spectrum of Fe³⁺ in a single crystal of forsterite was studied. Two distinct patterns of about equal intensities were observed which are due to Fe³⁺ at two distinct positions with 4a (M1)and4c (M2or Si) symmetry of Pbnm. The assignment of the 4c pattern to Fe³⁺ ions at the Si position cannot be excluded by symmetry but it is unlikely. The Hamiltonian parameters A and E/D are consistent with the conclusion that Fe³⁺ in this crystal is disordered over two distinct octahedral positions.  相似文献   

A M?ssbauer effect study of Fe³⁺ bearing γ-Fe₂SiO₄     

Zhe Li  I. Shinno  Danian Ye  Pingqiu Fu  Yueming Zhang 《中国科学D辑(英文版)》2001,44(1):34-46

Three synthetic Fe³⁺ bearing λ-Fe₂SiO₄ were analyzed using electron probe method, and the M?ssbauer spectra of the samples at 298 K, 150 K, and 95 K were measured. Each spectrum at three temperatures is composed of two doublets. These two doublets are assigned to Fe²⁺ in the octahedral sites and Fe³⁺ in the tetrahedral sites, respectively. Site occupancies were determined. The results show that Fe³⁺ and a small amount of Si⁴⁺ are in the tetrahedral and octahedral sites, respectively. The average bond lengths of the octahedral and tetrahedral sites were calculated according to the equations primarily given by Hill et al., O’Neill and Navrotsky and modified by the authors. Furthermore, the octahedral and tetrahedral bond lengths were used to calculate cell parameters and oxygen parameters. In addition, Fe³⁺ line broadening in the M?ssbauer spectra of Fe³⁺ bearing λ-Fe₂SiO₄ were interpreted by using the next nearest neighbor effects  相似文献   

Calorimetric study of the stability of high pressure phases in the systems CoOSiO₂ and “FeO”SiO₂, and calculation of phase diagrams in MOSiO₂ systems     

Alexandra Navrotsky  Faivel S. Pintchovski  Syun-Iti Akimoto 《Physics of the Earth and Planetary Interiors》1979,19(4):275-292

High temperature calorimetric measurements of the enthalpies of solution in molten if2 PbO · B₂O₃ of α- and γ-Fe₂SiO₄ and α-, β-, and γ-Co₂SiO₄ permit the calculation of phase relations at high pressure and temperature. The reported triple point involving α-, β-, and γ-Co₂SiO₄ is confirmed to represent stable equilibrium. The curvature in the α?β phase boundary in Co₂SiO₄ and of an α?γ boundary in Fe₂SiO₄ at high temperature is explained in part by the effects of compressibility and thermal expansion, but better agreement with the observed phase diagram is obtained when one considers the effect of small amounts of cation disorder in the spinel and/or modified spinel phases. The calculated ΔH⁰ and ΔS⁰ values for the α?β, α?γ, and β?γ transitions show that enthalpy and en changes both vary strongly in the series Mg, Fe, Co, and Ni, and are of equal importance in determining the stability relations. The disproportionation of Fe₂SiO₄ and Co₂SiO₄ spinel to rocksalt plus stishovite is calculated to occur in the 170–190 kbar region; cation disorder and/or changes in wüstite stoichiometry can affect the P?T slope. The calorimetric data for CoSiO₃ and FeSiO₃ are in good agreement with the observed phase boundary for pyroxene formation from olivine and quartz. The decomposition of pyroxene to spinel and stishovite at pressures near the coesite-stishovite transition is predicted in both iron and cobalt systems. The use of calorimetric data, obtained from small samples of high pressure phases, is very useful in predicting equilibrium phase diagrams in the 50–300 kbar range.  相似文献   

Fe³⁺ in shocked olivine crystals of the ALHA 77005 meteorite     

R. Ostertag  G. Amthauer  H. Rager  H.Y. McSween 《Earth and Planetary Science Letters》1984,67(2):162-166

ALHA 77005, a shocked achondrite of the shergottite group, is unique in containing cumulus olivine crystals which display a brownish color in thin section. Mössbauer, EPR, and optical spectroscopic studies show the presence of Fe³⁺ in the olivine. Approximately 4.5 wt.% of the total iron in the olivine (24 wt.% as FeO) is in the trivalent state. The Fe³⁺ ions preferentially occupy M2 lattice positions. Charge transfer between Fe³⁺ and Fe²⁺ as well as between Fe³⁺ and oxygen ligands causes a broad absorption band in the optical spectrum at high energies which is the reason for the olivine color. It is concluded that the color of the ALHA 77005 olivine is preterrestrial and may be the result of shock-induced oxidation of the olivine crystals on the meteorite parent body.  相似文献   

Electrical conductivity of magmatic liquids: effects of temperature,oxygen fugacity and composition     

Harve S. Waff  Daniel F. Weill 《Earth and Planetary Science Letters》1975,28(2):254-260

The effects of temperature, f_O2 and composition on the electrical conductivity of silicate liquids have been experimentally determined from 1200 to 1550°C under a range of f_O2 conditions sufficient to change the oxidation state of Fe from predominantly Fe²⁺ to Fe³⁺. Oxidation of ferrous to ferric iron in the melt has no measurable effect on the conductivity of melts with relatively low ratios of divalent to univalent cations. Under strongly oxidizing conditions a minor decrease of conductivity is detected inth highΣM²/ΣM⁺ ratios. It is concluded that for purposes of estimating the conductivity of magmatic liquids, f_O2 may be ignored to a first approximation. Both univalent and divalent cation transport is involved in electrical conduction. Melts relying heavily on divalent cations for conduction, i.e. melts with relatively large ΣM²⁺/ΣM⁺ ratios, show strong departures from Arrheenius temperature dependence with the apparent activation energies decreasing steadily as the temperature increases. Conductivities dominated by the univalent cations, in melts with relatively small ΣM²⁺/ΣM⁺ ratios, show classical Arrhenius temperature dependence. These observations are discussed in terms of the general characteristics of the melt structure.Compositional variations within the magmatic range account for much less than an order of magnitude variation in electrical conductivity at a fixed temperature. This observation, combined with previous measurements of the conductivity of olivine (A. Duba, H.C. Heard and R. Schock, 1974) make it possible to state with reasonable confidence that melts occurring within the mantle will be more conductive by 3–4 orders of magnitude than their refractory residues. Potential applications to geothermometry are discussed.  相似文献   

Elasticity of (Mg, Fe)(Si, Al)O₃-perovskite at high pressure     

Li Li  John P. Brodholt  Donald J. Weidner  Maria Alfredsson 《Earth and Planetary Science Letters》2005,240(2):529-536

The most abundant mineral on Earth has a perovskite crystal structure and a chemistry that is dominated by MgSiO₃ with the next most abundant cations probably being aluminum and ferric iron. The dearth of experimental elasticity data for this chemically complex mineral limits our ability to calculate model seismic velocities for the lower mantle. We have calculated the single crystal elastic moduli (c_ij) for (Mg, Fe^3 +)(Si, Al)O₃ perovskite using density functional theory in order to investigate the effect of chemical variations and spin state transitions of the Fe³⁺ ions. Considering the favored coupled substitution of Mg²⁺-Si^4 + by Fe³⁺-Al³⁺, we find that the effect of ferric iron on seismic properties is comparable with the same amount of ferrous iron. Ferric iron lowers the elastic moduli relative to the Al charge-coupled substitution. Substitution of Fe³⁺ for Al³⁺, giving rise to an Fe/Mg ratio of 6%, causes 1.8% lower longitudinal velocity and 2.5% lower shear velocity at ambient pressure and 1.1% lower longitudinal velocity and 1.8% lower shear velocity at 142 GPa. The spin state of the iron for this composition has a relatively small effect (< 0.5% variation) on both bulk modulus and shear modulus.  相似文献   

巢湖南淝河口黑水团区流速和溶解氧与Fe²⁺、S^2-浓度的空间关联性     

王玉琳  汪靓  华祖林  丁士明 《湖泊科学》2016,28(4):710-717

黑臭现象在我国东部地区浅水湖泊频繁发生,已经严重影响环湖地区的社会经济发展.厌氧环境和高浓度Fe~(2+)、S~(2-)是引起黑臭现象的必要条件.本文解析巢湖南淝河口区黑臭水团范围内Fe~(2+)、S~(2-)与DO、流速的分布特性;基于空间计量模型重点探讨了流速、DO和Fe~(2+)、S~(2-)分布的空间关联性.结果发现,水体流动在黑臭水团中主要有两个作用:使Fe~(2+)、S~(2-)和DO彼此产生空间相关性以及通过分散作用改变局部Fe~(2+)、S~(2-)浓度分布;同时流速通过增强复氧间接影响Fe~(2+)及S~(2-)总体浓度的作用较小.流速与Fe~(2+)、S~(2-)之间均满足线性空间滞后模型;而线性回归模型中流速对Fe~(2+)的影响低估了约7%,对S~(2-)的影响则低估了12%.  相似文献   

⁸⁷Sr/⁸⁶Sr ratios for basalt from Loihi Seamount,Hawaii     

Marvin Lanphere 《Earth and Planetary Science Letters》1983

⁸⁷Sr/⁸⁶Sr ratios of 15 samples of basalt dredged from Loihi Seamount range from 0.70334 to 0.70368. The basalt types range from tholeiite to basanite in composition and can be divided into six groups on the basis of abundances of K₂O, Na₂O, Rb and Sr and ⁸⁷Sr/⁸⁶Sr ratio. The isotopic data require that the various basalt types be derived from source regions differing in Sr isotopic composition. The Loihi basalts may be produced by mixing of isotopically distinct sources, but the tholeiites and alkalic basalts from Loihi do not show a well-developed inverse trend between Rb/Sr and ⁸⁷Sr/⁸⁶Sr that is characteristic of the later stages of Hawaiian volcanoes such as Haleakala and Koolau.  相似文献   

Spinel disproportionation at high pressure: calorimetric determination of enthalpy of formation of Mg₂SnO₄ and Co₂SnO₄ and some implications for silicates     

Alexandra Navrotsky  Robert B. Kasper 《Earth and Planetary Science Letters》1976,31(2):247-254

The enthalpies of formation from the oxides of Mg₂SnO₄ and Co₂SnO₄ were found by oxide melt solution calorimetry to be +1.13 ± 0.48 kcal/mol and ?2.31 ± 0.28 kcal/mol, respectively. Using these data, the slopes, ?P/?T, for disproportionation of these spinels to the component oxides at high pressure were calculated to be +30.4 ± 4.2 bar/K for Mg₂SnO₄ and ?10.3 ± 2.4 bar/K for Co₂SnO₄, in general agreement with the data of Jackson et al. (1974a,b). Using thermochemical data for the formation of olivines, for olivine-spinel transitions and for the transformation of quartz to stishovite, we calculate pressures for the disproportionation of silicate spinels to be in the range 150–200 kbar. Calculated slopes ?P/?T for the disproportionation reactions are ?10.7, ?24.9, ?11.2, and +7.6 bar/K for Mg₂SiO₄, Fe₂SiO₄, Co₂SiO₄, and Ni₂SiO₄. The large negative slope calculated for Fe₂SiO₄ results from a surprisingly large positive slope reported for the olivine-spinel transition in that compound (Akimoto et al., 1969). Further consideration of the systematic trends in the thermodynamics of spinel formation from the oxides suggests that the silicate spinels should have entropies of formation close to zero, resulting in values of ?P/?T which are zero or at most only slightly negative. This confirms the conclusion of Jackson, Liebermann, and Ringwood that values of ?P/?T for spinel disproportionation are unlikely to be more negative than ?10 bar/K and may well be slightly positive. Reaction of spinels to form other post-spinel phases, particularly ilmenite and perovskite, are discussed in terms of available thermochemical data.  相似文献   

Chemical variations in assemblages including epidote and/or chlorite in the fossil hydrothermal system of Saint Martin (Lesser Antilles)     

D. Beaufort  P. Patrier  A. Meunier  M.M. Ottaviani 《Journal of Volcanology and Geothermal Research》1992,51(1-2)

Epidote and/or chlorite are common minerals in the roots of the fossil geothermal system of Saint Martin (Lesser Antilles). They appear in four distinct assemblages: (1) epidote+actinolite+quartz±magnetite near the contact between the tuffaceous host rocks (andesitic modal composition) and the quartz-diorite intrusion of Philipsburg; (2) epidote+chlorite+quartz in host rocks as far as a lateral distance of about 3 km from the intrusion; (3) epidote+chlorite+haematite+quartz locally in iron and manganese rich host rocks; (4) chlorite±phengite±magnetite appearing as late sealing of porosity in fracture-controlled quartz veins with strongly phengitized wall rocks. All these assemblages constitute a large alteration grading from propylitic alteration to thermal metamorphism (actinolite-bearing assemblage).Detailed microprobe studies of epidotes replacing plagioclases and of chlorites replacing glass and mafic minerals reveal notable compositional variations which have been studied with respect to temperature paleogradients (estimated from fluid inclusions study), distance from the thermal source and f_o2 conditions. The mean Ps+Pm [100 × (Fe³⁺ + Mn³⁺)/(Al³⁺ + Fe³⁺ + Mn³⁺)] of epidotes vary from 21 in the presence of magnetite near the intrusion to 32 in haematite-bearing iron and/or manganese volcanic and sedimentary formations. The intra-grain chemical scattering of epidotes increases with increasing distance of the pluton and decreasing temperature of crystallization. All the chlorites coexisting with epidote are Mg-rich (X_Fe<0.50). Their main compositional variation consists in a significant enrichment in magnesium (toward the chlinochlore end member) in presence of haematite. The intra-grain chemical scattering of chlorite (expressed by the aluminium content in the structural formula) increases with increasing distance of the pluton and decreasing temperature of crystallization. Chlorites associated with phengite and magnetite in vein alteration are Fe- and Al-rich. The Mössbauer spectra indicate that the Fe³⁺ content of chlorite varies between 25 and 32% of total Fe in the presence of epidote; the higher content being attained in the presence of haematite. The Fe³⁺ content of chlorite associated with magnetite and phengite is 16% of total Fe. The compositional variations of epidote and/or chlorite of the four distinct assemblages observed at Saint Martin result from the combined effects of f_O2, temperature, and time of heating. The effect of f_O2 is particularly perceptible in the control of the epidote Ps content, of the chlorite X_Fe ratio of Fe³⁺ distribution between coexisting epidotes and chlorites. Despite the fact that it may be partially canceled out by the effect of f_O2, the variation of compositional ranges of both epidotes and chlorites, which increases toward the outer part of the geothermal system in response to the combination of decreasing temperatures and decreasing time of heating of the rocks, suggests that chemical equilibrium has not been attained in the assemblages bearing epidotes and chlorites.  相似文献   

Iron ions Fe<Superscript>2+</Superscript> and Fe<Superscript>3+</Superscript> in a magnetic model of the sedimentary medium     

V. E. Istomin  A. D. Duchkov 《Izvestiya Physics of the Solid Earth》2008,44(5):421-426

The concentration of rock-forming elements, the static magnetic susceptibility κ, spectra of electron paramagnetic resonance, and their relative intensities I are studied in samples from a borehole drilled in Cenozoic sedimentary deposits of southern Western Siberia. All measured values experience appreciable irregular variations with depth. A linear dependence exists between κ and I within the range of their medium and large values; κ and I have maximum values in the same sample, and κ_max = 1920 × 10^?6SI, κ_min = 210 × 10^?6 SI, and κ_av = 630 × 10^?6 SI. The magnetic properties of the samples are controlled by Fe²⁺ ions present in clastic material and by microphases (clusters) with Fe³⁺ ions of the goethite and lepidocrocite type present in the cement. The theoretically possible magnetic susceptibility of the Fe²⁺ ion system (provided that all iron exists in this form) is quite comparable with κ_min but, even with very high concentrations of Fe²⁺, does not reach half of κ_av: (154 < κ(Fe²⁺) < 254) × 10^?6 SI. Anomalously high values of κ are due to a large number of clusters with Fe³⁺ ions if structural units FeOOH do not dissociate and the interaction of the clusters with hydroxides of aluminum and precipitation medium impedes the process of their coagulation. Otherwise, the cluster sizes gradually increase, an antiferromagnetic structure develops in clusters, and the magnetic susceptibility decreases.  相似文献   

Synthesis of γ-Mg₂SiO₄     

Eiji Ito  Yoshito Matsui  Kaichi Suito  Naoto Kawai 《Physics of the Earth and Planetary Interiors》1974,8(4):342-344

Magnesium orthosilicate with spinel structure (γ-Mg₂SiO₄) was synthesized at about 250 kbar and 1000°C. Unit cell dimension was established to be 8.076 ± 0.001Å. X-ray powder diffraction pattern revealed a significant difference between γ-Mg₂SiO₄ and other γ-M₂SiO₄ spinels (M = Fe, Co, and Ni) in the intensities of (111) and (331) reflections, both of which are virtually absent in the Mg₂SiO₄ spinel. This feature could be thoroughly understood by the calculation of the intensities for several silicate spinels.  相似文献   

Iron oxidation state in lower mantle mineral assemblages: II. Inclusions in diamonds from Kankan, Guinea     

C.A McCammon  T Stachel 《Earth and Planetary Science Letters》2004,222(2):423-434

Inclusions of ferropericlase and former (Mg,Fe)(Si,Al)O₃ perovskite in diamonds from Kankan, Guinea believed to originate in the lower mantle were studied using Mössbauer spectroscopy to determine Fe³⁺/ΣFe. Fe³⁺ concentration in the (Mg,Fe)(Si,Al)O₃ inclusion is consistent with empirical relations relating Fe³⁺/ΣFe to Al concentration, supporting the inference that it crystallised in the perovskite structure at lower mantle conditions. In ferropericlase there is a nearly linear variation of trivalent cation abundance with monovalent cation abundance, suggesting a substitution of the form Na_0.5M_0.5³⁺O (M=Fe³⁺, Cr³⁺, Al³⁺). Excess positive charge is likely balanced by cation vacancies, where their abundance is observed to increase with increasing iron concentration, consistent with high-pressure experiments. The abundance of cation vacancies is related to oxygen fugacity, where ferropericlase inclusions from Kankan and São Luiz (Brazil) are inferred to have formed at conditions more oxidising than Fe-(Mg,Fe)O equilibrium, but more reducing than Re-ReO₂ equilibrium. Fe²⁺/Mg partition coefficients between (Mg,Fe)(Si,Al)O₃ and ferropericlase were calculated for inclusions co-existing in the same diamond using Mössbauer data and empirical relations based on high-pressure experimental work. Most values are consistent with high-pressure experiments, suggesting that these inclusions equilibrated at lower mantle conditions. The measured ferropericlase Fe³⁺ concentrations are consistent with diamond formation in a region of redox gradients, possibly arising from the subduction of oxidised material into reduced lower mantle. Reduction of carbonate to form ferropericlase and diamond is consistent with a slight shift of Kankan δ¹³C values to isotopically heavy compositions compared to the worldwide dataset, and could supply the oxygen necessary to satisfy the high Fe³⁺ concentration in (Mg,Fe)(Si,Al)O₃ perovskite, as well as account for the high proportion of ferropericlase in the lower mantle paragenesis. The heterogeneity of lower mantle diamond sources indicates that the composition of lower mantle diamonds do not necessarily reflect those of the bulk mantle.  相似文献   

The structure and sharpness of (Mg,Fe)₂SiO₄ phase transformations in the transition zone     

Daniel J. Frost 《Earth and Planetary Science Letters》2003,216(3):313-328

To calculate accurately the pressure interval and mineral proportions (i.e. yields) across the olivine to wadsleyite and wadsleyite to ringwoodite transformations requires a detailed knowledge of the non-ideality of Fe-Mg mixing in these (Mg,Fe)₂SiO₄ solid solutions. In order to constrain the activity-composition relations that describe non-ideal mixing, Fe-Mg partitioning experiments have been conducted between magnesiowüstite and (Mg,Fe)₂SiO₄ olivine, wadsleyite and ringwoodite as a function of pressure at 1400°C. Using known activity-composition relations for magnesiowüstite the corresponding relations for the three polymorphs were determined from the partitioning data. In all experiments the presence of metallic iron ensured redox conditions compatible with the Earth’s transition zone. The non-ideality of the (Mg,Fe)₂SiO₄ solid solutions was found to decrease in the order W^wadsleyite_FeMg>W^ringwoodite_FeMg>W^olivine_FeMg. These partitioning data were used, along with published phase equilibria measurements for the Mg₂SiO₄ and Fe₂SiO₄ end-member transformations, to produce an internally consistent thermodynamic model for the Mg₂SiO₄-Fe₂SiO₄ system at 1400°C. Using this model the pressure interval of the olivine to wadsleyite transformation is calculated to be significantly smaller than previous determinations. By combining these results with Fe-Mg partitioning data for garnet, the widths of transition zone phase transformations in a peridotite composition were calculated. The olivine to wadsleyite transformation at 1400°C in dry peridotite was found to occur over a pressure interval equivalent to approximately 6 km depth and the mineral yields were found to vary almost linearly with depth across the transformation. This transformation is likely to be even sharper at higher temperatures or could be significantly broader in wet mantle or in regions with a significant vertical component of mantle flow. The entire range of estimated widths for the 410 km discontinuity (4-35 km) could, therefore, be explained by the olivine to wadsleyite transformation in a peridotite composition over a range of quite plausible mantle temperatures and H₂O contents. The wadsleyite to ringwoodite transformation in peridotite mantle was calculated to take place over an interval of 20 km at 1400°C. This transformation yield was also found to be near linear.  相似文献   

Ni₂SiO₄-enthalphy of the olivine-spinel transition by solution calorimetry at 713°C     

Alexandra Navrotsky 《Earth and Planetary Science Letters》1973,19(4):471-475

The high pressure spinel polymorph of Ni₂SiO₄ persists metastably at 713°C and atmospheric pressure. The enthalpy of the olivine-spinel transition was obtained by measuring the heats of solution of both polymorphs in a molten oxide solvent, 2PbO · B₂O₃, at that temperature. For Ni₂SiO₄(ol)→Ni₂SiO₄, ΔH₉₈₆⁰ = +1.4 ± 0.7kcal/mol. The heat content increments, H₉₈₆ ? H₂₉₇, were found to be: olivine, 25.73 ± 0.42kcal/mol, and spinel, 25.39 ± 0.20kcal/mol. The measured enthalpy of the transformation is consistent with the low slope of the phase boundary, ?P/?T = ～ 12b/deg, observed by Akimoto and others. The entropy of the olivine-spinel transition in Ni₂SiO₄ is accordingly about a factor of three smaller in magnitude (ΔS = ～ ?1cal/deg mol) than that for Co₂SiO₄,Fe₂SiO₄,Mg₂SiO₄or Mg₂GeO₄ (ΔS = ?3to?3.5cal/deg mol).  相似文献   

Distinguishing Iron-Reducing from Sulfate-Reducing Conditions   总被引：2，自引：0，他引：2  

by Francis H. Chapelle  Paul M. Bradley  Mary Ann Thomas  and Peter B. McMahon 《Ground water》2009,47(2):300-305

Ground water systems dominated by iron‐ or sulfate‐reducing conditions may be distinguished by observing concentrations of dissolved iron (Fe²⁺) and sulfide (sum of H₂S, HS^?, and S⁼ species and denoted here as “H₂S”). This approach is based on the observation that concentrations of Fe²⁺ and H₂S in ground water systems tend to be inversely related according to a hyperbolic function. That is, when Fe²⁺ concentrations are high, H₂S concentrations tend to be low and vice versa. This relation partly reflects the rapid reaction kinetics of Fe²⁺ with H₂S to produce relatively insoluble ferrous sulfides (FeS). This relation also reflects competition for organic substrates between the iron‐ and the sulfate‐reducing microorganisms that catalyze the production of Fe²⁺ and H₂S. These solubility and microbial constraints operate in tandem, resulting in the observed hyperbolic relation between Fe²⁺ and H₂S concentrations. Concentrations of redox indicators, including dissolved hydrogen (H₂) measured in a shallow aquifer in Hanahan, South Carolina, suggest that if the Fe²⁺/H₂S mass ratio (units of mg/L) exceeded 10, the screened interval being tapped was consistently iron reducing (H₂～0.2 to 0.8 nM). Conversely, if the Fe²⁺/H₂S ratio was less than 0.30, consistent sulfate‐reducing (H₂～1 to 5 nM) conditions were observed over time. Concomitantly high Fe²⁺ and H₂S concentrations were associated with H₂ concentrations that varied between 0.2 and 5.0 nM over time, suggesting mixing of water from adjacent iron‐ and sulfate‐reducing zones or concomitant iron and sulfate reduction under nonelectron donor–limited conditions. These observations suggest that Fe²⁺/H₂S mass ratios may provide useful information concerning the occurrence and distribution of iron and sulfate reduction in ground water systems.  相似文献   

Petrologic properties of the upper 670 km of the earth's mantle; geophysical implications     

Thomas J. Ahrens 《Physics of the Earth and Planetary Interiors》1973,7(2):187-198

  相似文献   

Iron oxidation state in lower mantle mineral assemblages: I. Empirical relations derived from high-pressure experiments     

C.A. McCammon  S. Lauterbach  F. Seifert  P.A. van Aken 《Earth and Planetary Science Letters》2004,222(2):435-449

The oxidation state of iron can significantly influence the physical and chemical properties of lower mantle minerals. To improve methods for estimation of Fe³⁺/∑Fe, synthetic assemblages of (Mg,Fe)(Si,Al)O₃ perovskite and (Mg,Fe)O ferropericlase were synthesised from oxide starting mixtures in Re or Fe capsules at 26 GPa and 1650-1850 °C using a multianvil press. (Mg,Fe)(Si,Al)O₃ majorite was also present in some of the run products. Both electron energy loss spectra (EELS) and Mössbauer spectra were measured for each run product, and a robust fitting method was developed for Mössbauer spectra using EELS results as a standard that enabled Fe³⁺/∑Fe of (Mg,Fe)(Si,Al)O₃ perovskite to be determined from Mössbauer spectra of multiphase assemblages. There is a close to linear variation between Fe³⁺/∑Fe and Al concentration in (Mg,Fe)(Si,Al)O₃ perovskite, independent of oxygen fugacity. The concentration of Fe³⁺ in (Mg,Fe)O increases with increasing iron concentration along curves of constant oxygen fugacity, where higher oxygen fugacity stabilises greater Fe³⁺ concentrations. Fe²⁺/Mg partition coefficients calculated from chemical composition data corrected for measured Fe³⁺/∑Fe showed values nearly identical within experimental error for all samples, and independent of Al concentration and oxygen fugacity. Simple empirical relations were derived to calculate Fe³⁺/∑Fe in (Mg,Fe)(Si,Al)O₃ perovskite and (Mg,Fe)O ferropericlase samples for which no Mössbauer or EELS data were available, and tested by applying them to calculation of Fe²⁺/Mg partition coefficients from literature data for (Mg,Fe)(Si,Al)O₃ perovskite-(Mg,Fe)O assemblages where only total iron concentrations had been measured. Results showed Fe²⁺/Mg partition coefficients that were equal to existing values within experimental error, hence confirming the validity of the empirical relations.  相似文献   

The TiO₂–K₂O–P₂O₅ diagram: A method of discriminating between oceanic and non-oceanic basalts     

T.H. Pearce  B.E. Gorman  T.C. Birkett 《Earth and Planetary Science Letters》1975,24(3):419-426

The TiO₂–K₂O–P₂O₅ ternary diagram is proposed as a method of discriminating between oceanic and non-oceanic (continental) basalts. This diagram is effective for non-alkaline “primitive” basalts: fractionated rocks cannot be adequately discriminated. Suitable analyses are those which have total alkalies ≤ 20% in an (Fe₂O₃ + FeO)–MgO–(Na₂O + K₂O) diagram. The proposed dividing line separates 93% of 222 ocean-floor and ocean-ridge basalts into the oceanic field and > 80% of continental basalt analyses into the non-oceanic field. Two exceptions are the Tertiary basalts of Greenland and the Deccan Traps which have oceanic affinities. “Continental” suites displaying an oceanic affinity in the TiO₂–K₂O–P₂O₅ diagram may be a result of abortive attempts to generate new sea floor. Preliminary results for dike swarms and Archean basalts suggest preponderant oceanic affinities. Alteration and metamorphism of oceanic basalts generally occasion enrichment of K₂O relative to TiO₂ and P₂O₅.  相似文献