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   

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   

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   

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   

Oxidation state of iron in plagioclase from lunar basalts     

S.S. Hafner  D. VirgoD. Warburton 《Earth and Planetary Science Letters》1971

Mossbauer spectra of⁵⁷Fe at 77 and 295°K in the plagioclase from basalts 10044 and 12021 show that iron is in the high-spin ferrous state and located at at least two distinct positions with different coordination numbers. Some excess resonant absorption is probably due to Fe³⁺ although the Fe³⁺ doublet could not be positively resolved. The ratio Fe³⁺/(Fe²⁺ + Fe³⁺) is estimated to be between 0.02 and 0.1.  相似文献   

Co²⁺ as a chemical analogue for Fe²⁺ in high-temperature experiments in basaltic systems     

William E. Coons  John R. Holloway  Alexandra Navrotsky 《Earth and Planetary Science Letters》1976,30(2):303-308

High-temperature experiments on ferromagnesian compositions have been hampered by the rapid absorption of up to 95% of the original iron by platinum and 40% by silver-palladium capsules. Molybdenum or iron capsule materials can decrease or alleviate iron loss, but restrict oxygen fugacities to values near the iron-wustite buffer. Because Co²⁺ is stable at f_O2 =HM and because the solubility of Co in platinum in this range of f_O2 is ～0.05% at temperatures to 1350°C, its use as an analogue for Fe²⁺ is possible. In addition, experiments simulating various Fe²⁺ ratios can be easily performed by choosing appropriate Co²⁺/Fe³⁺ ratios. The cobalt phases produced possess brilliant and distinctive colors which are valuable aids in optical identification of minute phases. The cobalt analogue hypothesis was tested with atmospheric pressure experiments in air on the cobalt analogue of the 1921 Kilauea basalt at three simulated Fe²⁺/Fe³⁺ ratios. The results were compared with those of R.E.T. Hill (1969) for the natural 1921 basalt. The phase relations were the same, with the cobalt system stability fields systematically shifted by about +50°C. Microprobe analysis of olivines and the coexisting glasses indicate that the distribution of Co²⁺ between olivine and melt is independent of temperature and liquid composition. Although the analogue liquid composition differs from the equilibrium composition of the natural system, it may be corrected be employing distribution coefficients (K_D = 0.61 for the Co system; K_D = 0.33 for the Fe system) to closely approximate what the natural system would yield if iron loss did not occur.  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   

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   

Spin state of ferric iron in MgSiO3 perovskite and its effect on elastic properties     

Krystle Catalli  Sang-Heon Shim  Vitali B. Prakapenka  Jiyong Zhao  Wolfgang Sturhahn  Paul Chow  Yuming Xiao  Haozhe Liu  Hyunchae Cynn  William J. Evans 《Earth and Planetary Science Letters》2010,289(1-2):68-75

Recent studies have indicated that a significant amount of iron in MgSiO₃ perovskite (Pv) is Fe³⁺ (Fe³⁺/ΣFe = 10–60%) due to crystal chemistry effects at high pressure (P) and that Fe³⁺ is more likely than Fe²⁺ to undergo a high-spin (HS) to low-spin (LS) transition in Pv in the mantle. We have measured synchrotron Mössbauer spectroscopy (SMS), X-ray emission spectroscopy (XES), and X-ray diffraction (XRD) of Pv with all iron in Fe³⁺ in the laser-heated diamond-anvil cell to over 100 GPa. Fe³⁺ increases the anisotropy of the Pv unit cell, whereas Fe²⁺ decreases it. In Pv synthesized above 50 GPa, Fe³⁺ enters into both the dodecahedral (A) and octahedral (B) sites approximately equally, suggesting charge coupled substitution. Combining SMS and XES, we found that the LS population in the B site gradually increases with pressure up to 50–60 GPa where all Fe³⁺ in the B site becomes LS, while Fe³⁺ in the A site remains HS to at least 136 GPa. Fe³⁺ makes Pv more compressible than Mg-endmember below 50 GPa because of the gradual spin transition in the B site together with lattice compression. The completion of the spin transition at 50–60 GPa increases bulk modulus with no associated change in density. This elasticity change can be a useful seismic probe for investigating compositional heterogeneities associated with Fe³⁺.  相似文献   

Iron-magnesium order-disorder in an orthopyroxene crystal from the Johnstown meteorite     

G.M. Molin  S.K. Saxena  E. Brizi 《Earth and Planetary Science Letters》1991,105(1-3)

Equilibrium reversals of Fe²⁺Mg distribution between the M1 and M2 sites of an orthopyroxene from the Johnstown meteorite were achieved at several temperatures between 700 and 1000°C. One single crystal was used for the whole thermal treatment and for collecting all the X-ray data after quenching. The intracrystalline ion exchange for the bulk chemical composition: (Mg_1.453Fe_0.441Cr_0.024Ca_0.054Mn_0.015Fe_0.005Ti_0.003Al_0.005)(Si_1.960Al_0.040)O₆ is given by: ln K_D = −3027(±39)/T(K) + 0.872(±0.013)> where K_D is the distribution coefficient for the reaction: Fe_M2²⁺ + Mg_M1 = Mg_M2 + Fe_M1²⁺.A transmission electron microscopy (TEM) study of part of the crystal showed the presence of very thin augite lamellae and Guinier-Preston zones indicating a relatively rapid cooling of the host rock at temperatures close to 1000°C. The new temperature scale yields a relatively high quenching temperature of 379 (±8)°C for the pyroxene which appears consistent with a rapid cooling (estimated few degrees per hundred years) of a magmatic cumulate excavated by an impact on its parental body.  相似文献   

Influence of the crystal field effect on chemical transport in Earth's mantle: Cr3+ and Ga3+ diffusion in periclase     

Katherine L. Crispin  James A. Van Orman 《Physics of the Earth and Planetary Interiors》2010,180(3-4):159-171

Experiments were performed to determine concentration-dependent diffusion coefficients of Cr³⁺ and Ga³⁺ in periclase at temperatures of 1563–2273 K. Diffusion profiles measured in the quenched samples are consistent with a theoretical model in which the mobile species is a bound M³⁺-vacancy pair, and each profile was fitted to determine the binding energy and diffusion coefficient of the pair. Trivalent chromium-vacancy pairs diffuse more slowly than Ga³⁺-vacancy pairs, and with higher migration energy, 237 kJ/mol vs. 190 kJ/mol. Cation vacancies also bind less tightly to Cr³⁺ than to Ga³⁺, with average binding free energies of ?22 and ?83 kJ/mol, respectively. At all concentrations and temperatures, Cr³⁺ diffuses much more slowly than Ga³⁺, by up to two orders of magnitude. The differences between Cr³⁺ and Ga³⁺ cannot be explained by differences in ionic radius or dipole polarizability, but are consistent with the influence of the crystal field on the partially occupied 3d orbitals of Cr³⁺. The crystal field splitting stabilizes Cr³⁺ on the octahedral cation site, increasing the energy required for Cr³⁺ to exchange positions with an adjacent vacancy. It also makes Cr³⁺-vacancy pairs less favorable, with the presence of a nearest-neighbor vacancy disrupting the symmetry of the octahedral site, thus diminishing the crystal field stabilization. Trends in the diffusion of first-row divalent transition metals in periclase can also be explained by the crystal field effect. High-spin to low-spin transitions in Fe²⁺, Co²⁺ or Mn²⁺ would significantly enhance their crystal field stabilization in periclase, and if such spin transitions occur in the deep mantle, they would be expected to slow the diffusivity of these ions significantly, perhaps by several orders of magnitude.  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   

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   

Evolution of uranogenic and thorogenic lead, 2. Some differences in the variations of the²⁰⁶Pb/²⁰⁴Pb and²⁰⁸Pb/²⁰⁴Pb ratios     

Blagoi G. Amov 《Earth and Planetary Science Letters》1983,65(2):311-321

On the basis of a dynamic model of a continuous Pb isotope evolution, the variations in the isotopic ratios of uranogenic and thorogenic Pb in a number of young ore deposits, ocean sediments and volcanic rocks from mid-ocean ridges, oceanic islands, island arcs and continents are evaluated. The deviations in the Th/U ratio from its model values are calculated. A model parameterT which indicates a more ancient enrichment in U/Pb (crustal-type Pb sources) or younger enrichment in U/Pb (mantle-type Pb sources) is also calculated. The relative change in the Th/U ratio is close to 1 for mantle-type Pb sources (lowerT values) and decreases for crustal-type Pb sources (higherT values). An interpretation of these changes could be connected with the differences in the U and Th geochemical behaviours in metamorphic processes under the conditions of a deeper (mantle) or crustal source owing to the differences in their valence states. In some cases they have similar (U⁴⁺ and Th⁴⁺) migration abilities; in others (U⁶⁺ and Th⁴⁺), considerably different.  相似文献   

Crystal structure and compositional variation of Angra dos Reis fassaite     

Robert M. Hazen  Larry W. Finger 《Earth and Planetary Science Letters》1977,35(2):357-362

The crystal structure of fassaite from the Angra dos Reis meteorite has been determined by least-squares refinement of three-dimensional X-ray data to anR value of 3.3%. The pyroxene is monoclinic, space groupC2/c, with unit-cell dimensionsa = 9.738(1),b = 8.874(2),c = 5.2827(5)Å, β = 105.89(1)°, andV = 439.1(1)ų. Average bond lengths are (Si,Al)-O = 1.651, M1-O = 2.061, and M2-O = 2.489Å. The distribution of iron and magnesium between M1 and M2 suggests a temperature of equilibration greater than 1000°C.Electron microprobe analysis of several fassaite grains reveals small but statistically significant variations of (Mg + Si) versus (Al - Ti). The range of fassaite composition may be represented byEn₃Hd₂₂TiCpx₆(Di_53±2CaTs_16?2) whereEn=Mg₂Si₂O₆,Hd=CaFeSi₂O₆,TiCpx=CaTiAl₂O₆,Di=CaMgSi₂O₆,CaTs=CaAl₂SiO₆. Most fassaite analyses calculated on the basis of four cations yielded greater than six anions, suggesting that part of the titanium or chromium might be reduced to Ti³⁺ or Cr²⁺.  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   

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   

Cation distribution in low-calcium pyroxenes: Dependence on temperature and calcium content and the thermal history of lunar and terrestrial pigeonites     

Surendra K. Saxena  Subrata Ghose  A.C. Turnock 《Earth and Planetary Science Letters》1974,21(2):194-200

Four pyroxenes with compositions En₄₈Fs₄₈Wo₄, En_47·5Fs_47·5Wo₅, En₄₅Fs₄₅Wo₁₀ and En₄₀Fs₄₀Wo₂₀, synthesized at 1200°C at atmospheric pressure, were heat-treated at 500, 600, 700, and 800°C for various lengths of time. These pyroxenes are variously ordered with respect to Fe²⁺ and Mg²⁺ without unmixing. The Fe²⁺-Mg²⁺ distribution over the two nonequivalent sites M1 and M2, determined through Mössbauer spectroscopy, is found to be a function of both temperature and concentration of Ca²⁺ at the M2 site. The preference of Fe²⁺ for the M2 site increases with decreasing temperature and increasing Ca²⁺. These data can be used to determine cation equilibration temperatures of lunar and terrestrial pigeonites. The lunar pigeonites usually indicate equilibration temperatures of 700–860°C, except the pigeonite from rock 14053, which may have been subjected to shock heating due to meteoritic impact.  相似文献   

The effect of ferromagnetism on the equation of state of Fe₃C studied by first-principles calculations     

Lidunka Vo?adlo  John BrodholtDavid P Dobson  K.S Knight  W.G MarshallG.David Price  Ian G Wood 《Earth and Planetary Science Letters》2002,203(1):567-575

First-principles calculations have been used to determine the equation of state of Fe₃C in both its low-pressure magnetically ordered and high-pressure non-magnetically ordered states; at 0 K the ferromagnetic transition was found to occur at about 60 GPa. In the high pressure, non-magnetically ordered regime at 0 K the material may be described by a Birch-Murnaghan third-order equation of state with V₀=8.968(7) ų per atom, K₀=316.62(2) GPa and K′=4.30(2). At atmospheric pressure the ferromagnetic phase transition in Fe₃C occurs at ∼483 K; preliminary measurements of the thermal expansion by powder neutron diffraction show that this transition produces a large effect on thermoelastic properties. The volumetric thermal expansion coefficient in the paramagnetic phase was found to be 4.34×10⁻⁵ K⁻¹ at T∼550 K. By applying a thermal expansion correction to the calculated equation of state at 0 K, predicted values for the density and adiabatic incompressibility of this material at core pressures and temperatures were obtained. These results appear to be sufficiently different from seismological data so as to preclude Fe₃C as the major inner core-forming phase.  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