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   

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 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   

A new method to estimate the oxidation state of basaltic series from microprobe analyses     

Lydéric France  Benoit Ildefonse  Juergen Koepke  Florent Bech 《Journal of Volcanology and Geothermal Research》2010,189(3-4):340-346

The oxygen fugacity and therefore the iron redox state of a melt is known to have a strong influence on the liquid line of descent of magmas and thus on the composition of the coexisting melts and crystals. We present a new method to estimate this critical parameter from electron probe microanalyses of two of the most common minerals of basaltic series, plagioclase and clinopyroxene. This method is not based on stoichiometric calculations, but on the different partitioning behaviour of Fe³⁺ and Fe²⁺ between both minerals and a melt phase: plagioclase can incorporate more Fe³⁺ than Fe²⁺, while clinopyroxene can incorporate more Fe²⁺ than Fe³⁺. For example, the effect of oxidizing a partly molten basaltic system (Fe³⁺ is stabilized with respect to Fe²⁺) results in an increase of FeO_total in plagioclase, but a decrease in the associated clinopyroxene. We propose an equation, based on published partition coefficients, that allows estimating the redox state of a melt from these considerations. An application to a set of experimental and natural data attests the validity of the proposed model. The associated error can be calculated and is on average < 1 log unit of the prevailing oxygen fugacity.In order to reduce the number of different variables influencing the Fe²⁺/Fe³⁺ mineral/melt equilibrium, our model is restricted to basaltic series with SiO₂ < 60% that have crystallized at intermediate to low pressure (< 0.5 GPa) and under relatively oxidizing conditions (?FMQ > 0; where FMQ is the fayalite–magnetite–quartz oxygen buffer equilibrium), but it may be parameterized for other conditions. A spreadsheet is provided to assist the use of equations, and to perform the error propagation analysis.  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   

Seasonal and diurnal variation of electron and iron concentrations at the meteor heights above Arecibo     

《Journal of Atmospheric and Solar》2008,70(1):49-60

We report observations of seasonal and local time variation of the averaged electron and iron concentrations, as well as simultaneous measurements of the two species, above the Arecibo Observatory (18.35°N, 66.75°N), Puerto Rico. The average Fe profile between 21:00 and 24:00 LT has a single peak at about 85 km with the exception of the summer when an additional peak exists at about 95 km. The higher Fe peak in the summer is correlated with higher electron concentrations in this season. The three nights of simultaneous measurements of electron and iron concentrations show that narrow layers of Fe and electrons are well correlated. Comparison of the climatological and simultaneous Fe and electron data suggests that recombination of Fe⁺ plays an important role in determining the Fe profile in the upper part of the Fe layer. Above 93 km, the Fe concentration appears to increase after sunset if the electron concentration exceeds about 4000 electrons cm⁻³. The average rate of Fe production is about 0.1 atom cm⁻³ s⁻¹ for all seasons at 100 km in the early evening hours. A chemical model reveals that the concentration of Fe⁺ must be 50–80% of the total ionization over Arecibo for typical equinox conditions to explain the observed rate of Fe production. These high relative Fe⁺ concentrations are consistent with in situ observations that Fe⁺ is usually the dominant ion in sporadic E layers in the nighttime lower E region. This suggests that the source of Fe⁺ is provided by sporadic E layers descending over Arecibo after sunset. The Fe density between 80 and 85 km decreases during the night, for all seasons. This is attributed to the formation of stable molecular Fe species, such as FeOH, due to the increase in O₃ and decrease in atomic O and H during the night at these altitudes.  相似文献   

Thermal equation of state of magnesiowüstite (Mg0.6Fe0.4)O     

《Physics of the Earth and Planetary Interiors》2002,129(3-4):301-311

Volume measurements for magnesiowüstite (Mg_0.6Fe_0.4)O, were carried out up to pressures of 10.1 GPa in the temperature range 300–1273 K, using energy-dispersive synchrotron X-ray diffraction. These data allow reliable determination of the temperature dependence of the bulk modulus and good constraint on the thermal expansitivity at ambient pressure which was previously not known for magnesiowüstite. From these data, thermal and elastic parameters were derived from various approaches based on the Birch–Murnaghan equation of state (EOS) and on the relevant thermodynamic relations. The results from three different equations of state are remarkably consistent. With (∂K_T/∂P)_T fixed at 4, we obtained K₀=158(2) GPa, (∂K_T/∂T)_P=−0.029(3) GPa K⁻¹, (∂K_T/∂T)_V=−3.9(±2.3)×10⁻³ GPa K⁻¹, and α_T=3.45(18)×10⁻⁵+1.14(28)×10⁻⁸T. The K₀, (∂K_T/∂T)_P, and (∂K_T/∂T)_V values are in agreement with those of Fei et al. (1992) and are similar to previously determined values for MgO. The zero pressure thermal expansitivity of (Mg_0.6Fe_0.4)O is found to be similar to that for MgO (Suzuki, 1975). These results indicate that, for the compositional range x=0–0.4 in (Mg_1−xFe_x)O, the thermal and elastic properties of magnesiowüstite exhibit a dependence on the iron content that is negligibly small, within uncertainties of the experiments. They are consequently insensitive to the Fe–Mg partitioning between (Mg, Fe)SiO₃ perovskite and magnesiowüstite when applied to compositional models of the lower mantle. With the assumption that (Mg_0.6Fe_0.4)O is a Debye-like solid, a modified equation of heat capacity at constant pressure is proposed and thermodynamic properties of geophysically importance are calculated and tabulated at high temperatures.  相似文献   

Ab initio study of the composition dependence of the pressure-induced spin crossover in perovskite (Mg1 − x,Fex)SiO3     

Amelia Bengtson  Kristin Persson  Dane Morgan 《Earth and Planetary Science Letters》2008,265(3-4):535-545

We present ab initio calculations of the zero-temperature iron high- to low-spin crossover in (Mg_1 ? xFe_x)SiO₃ perovskite at pressures relevant to Earth's lower mantle. Equations of state are fit for a range of compositions and used to predict the Fe spin transition pressure and associated changes in volume and bulk modulus. We predict a dramatic decrease in transition pressure as Fe concentration increases. This trend is contrary to that seen in ferropericlase, and suggests the energetics for spin crossover is highly dependent on the structural environment of Fe. Both Local Density Approximation (LDA) and Generalized Gradient Approximation (GGA) exchange-correlation methods are used, and both methods reproduce the same compositional trends. However, GGA gives a significantly higher transition pressure than LDA. The spin transition is made easier by the decreasing spin-flip energy with pressure but is also driven by the change in volume from high to low spin. Volume trends show that high-spin Fe²⁺ is larger than Mg²⁺ even under pressure, but low-spin Fe²⁺ is smaller at ambient conditions and approximately the same size as Mg²⁺ under high pressure, indicating that low-spin Fe²⁺ is less compressible than high-spin Fe²⁺. We find large changes between high- and low-spin in the slope of volume with Fe concentration. Although these changes are small in absolute magnitude for small Fe content, they are still important when measured per Fe and could be relevant for calculating partitioning coefficients in the lower mantle.  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   

A reassessment of current volcanic emissions from the Central American arc with specific examples from Nicaragua     

《Journal of Volcanology and Geothermal Research》2006,149(3-4):297-311

The Central American volcanic arc supplies a significant proportion of the persistent annual global sulphur dioxide emissions from volcanoes. In November/December 2003, we completed a survey of the arc section from Mombacho to San Cristóbal in Nicaragua recording individual mean fluxes of 800, 530 and 220 Mg day^− 1 in the plumes from San Cristóbal, Telica and Masaya, respectively. An assessment of fluxes published since 1997 along the entire Central America arc yields a mean total arc flux of SO₂ of 4360 Mg day^− 1 or 8–16% of the annual estimated global volcanic SO₂ flux to the troposphere. New field data shows that Masaya volcano continues to show stable HCl/SO₂ and HF/SO₂ ratios, suggesting a sustained flux of these components of ∼ 220 and 30 Mg day^− 1, respectively (1997 to 2004). Masaya's plume composition also appears to have been stable, between 2001 and 2003, with respect to all the particulate species measured, with significant fluxes of SO₄²⁻ (4 Mg day^− 1), Na⁺ (0.9–1.3 Mg day^− 1) and K⁺ (0.7 Mg day^− 1). Extrapolating the Masaya plume species ratios to the entire Central American arc gives mean HCl and HF fluxes of 1300 and 170 Mg day^− 1 and a particulate sulphate flux of 40 Mg day^− 1 for 1997 to 2004, although without further understanding of the degassing processes and sources at depth of these different volatiles, these arc-scale estimates should be treated with caution. Combining our arc scale mean SO₂ flux with published measurements of volcanic gas compositions with respect to CO₂ and H₂O allows us to estimate mean CO₂ fluxes of 4400–9600 Mg day^− 1 and H₂O fluxes of 70,000–78,000 Mg day^− 1 for the arc. Preliminary comparisons of these estimates of outgassing rates with published volatile input fluxes into the Central American subduction zone, suggest that Cl is more efficiently recycled through the subduction zone than CO₂. The results for H₂O are inconclusive.  相似文献   

Dechlorination of 3,3′,4,4′-tetrachlorobiphenyl (PCB77) in water,by nickel/iron nanoparticles immobilized on L-lysine/PAA/PVDF membrane     

《Physics and Chemistry of the Earth》2013

In this study, the dechlorination of chlorinated hydrocarbon 3,3′,4,4′-tetrachlorobiphenyl (PCB77) by bimetallic Ni/Fe nanoparticles immobilized on L-lysine/PAA/PVDF membrane was investigated at ambient conditions through the batch mode operation. The membrane support polyvinylidene fluoride (PVDF) was modified by in situ polymerization of acrylic acid in aqueous phase, then L-lysine was covalently bonded to the polymerized acrylic acid chains with the aid of a water-soluble carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC). The modification procedure involved cationic ion exchange with Fe²⁺, reduction to Fe⁰ with NaBH₄ and finally deposition of Ni⁰. The scanning electron microscopic images showed that the Ni/Fe nanoparticles were successfully immobilized inside the membrane using the polyacrylic acid (PAA) as an inter-linkage between PVDF and L-lysine. A systematic characterization of the composite was performed using ATR-FTIR, HRSEM, EDX, HRTEM, XRD, and contact angle measurement studies and a relatively uniform distribution of Ni/Fe was found in L-lysine/PAA/PVDF membrane because of its hydrophilic nature. The obtained Ni/Fe nanoparticles consist of Fe⁰ core surrounded by the Ni⁰ shell. The diameter of Ni/Fe nanoparticles was predominantly within the range 20–30 nm. The immobilized Ni/Fe nanoparticles exhibited a good reactivity towards the dechlorination of the chlorinated hydrocarbon since the concentration of the PCB77 was decreased by catalytic dechlorination with Ni/Fe nanoparticles inside the L-lysine/PAA/PVDF membrane. Dechlorination efficiency of 98% was achieved within 9 h.  相似文献   

Magnesium isotopes constraints on the origin of Mg-rich olivines from the Allende chondrite: Nebular versus planetary?     

Johan Villeneuve  Marc Chaussidon  Guy Libourel 《Earth and Planetary Science Letters》2011,301(1-2):107-116

High precision Mg isotope measurements by multi-collector ion microprobe show that refractory olivines from the Allende chondrite, either olivines isolated in the matrix (2 samples studied) or olivines in type I chondrules (6 samples studied), have variable δ²⁶Mg* enrichments and deficits (calculated in permil as the ²⁶Mg deviation from the instrumental mass fractionation line) relative to the Earth. Most average δ²⁶Mg* (noted δ²⁶Mg*_av) values (between 10 and 20 analyses per chondrule) are negative but the total range is from ?0.029 (± 0.010) ‰ (2 sigma errors) to + 0.011 (± 0.011) ‰ with an exception of one olivine at + 0.043 (± 0.023) ‰. These variations in δ²⁶Mg*_av reflect the formation of the olivines from reservoirs enriched in various amounts of ²⁶Mg by the decay of short-lived ²⁶Al (T_1/2 = 0.73 Ma). Similarly, 30 analyses of olivines from the Eagle Station pallasite show a δ²⁶Mg*_av value of ?0.033 ± 0.008‰, as negative as some olivines from Allende chondrules and the Solar system initial δ²⁶Mg* value of ?0.038 ± 0.004‰ (defined at the time of formation of type B Ca–Al-rich inclusions – CAIs – when ²⁶Al/²⁷Al = 5.23 × 10^?5, Jacobsen et al., 2008).Because olivines are Al-poor and because their Mg isotopic compositions are not reset during the chondrule forming events, their δ²⁶Mg*_av can be used to calculate model crystallization ages relative to various theoretical Mg isotope growth curves. The two end-member scenarios considered are (i) a “nebular” growth in which the Al/Mg ratio remains chondritic and (ii) a “planetary” growth in which a significant increase of the Al/Mg ratio can be due to, for instance, olivine magmatic fractionation. The low δ²⁶Mg*_av value of olivines from the Eagle Station pallasite demonstrate that metal-silicate differentiation occurred as early as ~ 0. 15_- 0. 23^+ 0. 29 Ma after CAIs in either of the growth scenarios. Similarly the variable δ²⁶Mg*_av values of refractory olivines can be understood if they were formed in planetesimals which started to differentiate as early as the Eagle Station parent body. Accretion of these planetesimals must have been coeval to the formation of CAIs and their disruption could explain why their fragments (Mg-rich olivines) were distributed in the chondrule forming regions of the disk.  相似文献   

Aluminum incorporation in α-PbO2 type TiO2 at pressures up to 20 GPa     

Alberto Escudero  Falko Langenhorst 《Physics of the Earth and Planetary Interiors》2012

Aluminum incorporation into the high pressure polymorph of TiO₂ with the structure of α-PbO₂ has been studied from 10 to 20 GPa and 1300 °C by XRD, high-resolution ²⁷Al MAS-NMR and TEM. Al-doped α-PbO₂ type TiO₂ can be recovered at atmospheric pressure. Al₂O₃ solubility in α-PbO₂ type TiO₂ increases with increasing the synthesis pressure. The α-PbO₂ type TiO₂ polymorph is able to incorporate up to 35 wt.% Al₂O₃ at 13.6 GPa and 1300 °C, being the substitution of Ti⁴⁺ by Al³⁺ on normal octahedral sites the mechanism of solubility. The transition to the higher pressure TiO₂ polymorph with the ZrO₂ baddeleyite structure, Akaogiite, has not been observed in the quenched samples at room pressure. The microstructure of the recovered sample synthesized at 16 GPa and 1300 °C points to the existence of a non-quenchable aluminum titanium oxide phase at these conditions.  相似文献   

Stratification and mixing of a post-glacial Neoproterozoic ocean: Evidence from carbon and sulfur isotopes in a cap dolostone from northwest China     

Bing Shen  Shuhai Xiao  Alan J. Kaufman  Huiming Bao  Chuanming Zhou  Haifeng Wang 《Earth and Planetary Science Letters》2008,265(1-2):209-228

To improve our knowledge about the geochemical and environmental aftermath of Neoproterozoic global glaciations, we analyzed stable isotopes (δ¹³C, δ¹⁸O, δ³⁴S) and elemental concentrations (Ca, Mg, S, Sr, Fe, and Mn) of the ～ 10-m-thick Zhamoketi cap dolostone atop the Tereeken diamictite in the Quruqtagh area, eastern Chinese Tianshan. Available chemostratigraphic data suggest that the Tereeken diamictite is probably equivalent to the Marinoan glaciation. Our new data indicate that organic and carbonate carbon isotopes of the Zhamoketi cap dolostone show little stratigraphic variations, averaging ? 28.2‰ and ? 4.6‰, respectively. In contrast, sulfur isotopes show significant stratigraphic variations. Carbonate associated sulfate (CAS) abundance decreases rapidly in the basal cap dolostone and δ³⁴S_CAS composition varies between + 9‰ and + 15‰ in the lower 2.5 m. In the overlying interval, CAS abundance remains low while δ³⁴S_CAS rises ～ 5‰ and varies more widely between + 10‰ and + 21‰. The range of δ³⁴S_py of the cap dolostone overlaps with that of δ³⁴S_CAS, but direct comparison shows that δ³⁴S_py is typically greater than δ³⁴S_CAS measured from the same samples. Hypotheses to explain the observations must account for both the remarkable sulfur isotope enrichment of pyrites and the inverse fractionation. We propose that CAS and pyrite were derived from two isotopically distinct reservoirs in a chemically stratified basin or a basin with a sulfate minimum zone. In this model, CAS was derived from shallow, oxic surface waters with moderate sulfate concentration and depleted in ³⁴S due to the post-glacial influx of sulfur from continental weathering. In contrast, pyrite was derived from anoxic bottom waters (or a sulfate minimum zone) with low sulfate concentration and ³⁴S enrichment due to long-term syn-glacial sulfate reduction. The rapid shift in CAS abundance and sulfur isotope composition within the cap dolostone is interpreted to reflect the mixing of the two reservoirs after initial deglaciation. Comparison with other post-Marinoan cap carbonates shows significant spatial heterogeneity in δ³⁴S_CAS, which together with strong temporal variation in δ³⁴S_CAS, points to generally low sulfate concentrations in post-Marinoan oceans.  相似文献   

Cation distribution in synthetic titanomaghemites     

J.B. O&#x;Donovan  W. O&#x;Reilly 《Physics of the Earth and Planetary Interiors》1978,16(3):200-208

Because of the difficulties of laboratory simulation of maghemitization, few studies have been carried out and the results of such studies are not in good agreement. Of particular interest is the evolution of the cation distribution with degree of non-stoichiometry. This indicates how the maghemitization process takes place at the atomic level. In the present study a suite of titanomagnetite specimens containing a range of concentration of Mg²⁺ ions were maghemitized and the possible cation distribution inferred from saturation magnetization measurements. Although a unique cation distribution cannot be obtained from such measurements, the observed data are consistent with the following model, except for high degrees of oxidation and high Mg concentration: (1) Ti⁴⁺ and vacancies in B sites only; (2) a random distribution of Mg²⁺ which remains frozen in during maghemitization; (3) availability for oxidation of tetrahedral site Fe²⁺ 20% of that of octahedral site Fe²⁺; and (4) deficient moment of the oxidized specimens due to small particle size.  相似文献   

Elasticity of single crystal pyrope and implications for garnet solid solution series     

Barbara J. Leitner  Donald J. Weidner  Robert C. Liebermann 《Physics of the Earth and Planetary Interiors》1980,22(2):111-121

The elastic moduli of a synthetic single crystal of pyrope (Mg₃Al₂Si₃O₁₂) have been determined using a technique based on Brillouin scattering. These results are used in an evaluation of the effect of composition on the elastic properties of silicate garnet solid solution series (Mg, Fe, Mn, Ca)₃ (Al, Fe, Cr)₂ Si₃O₁₂. In the pyralspites (Mg FeMn aluminum garnets), for which a large amount of data is available, this analysis indicates that the bulk modulus K is independent of the Fe²⁺/Mg²⁺ ratio, which is similar to the behavior observed in olivines and pyroxenes. However, the shear modulus μ of the garnets increases by 10% from the Mg to the Fe end member, in contrast to the decrease of μ with Fe content which is observed in olivines and pyroxenes. This contrasting behavior is most probably related to the oxygen coordination of the cation site occupied by Mg²⁺ and Fe²⁺ in these different minerals.  相似文献   

A Mssbauer effect study of Fe³⁺ bearing     

LI Zhe  I.Shinno  YE Danian  FU Pingqiu  Zhang Yueming 《中国科学D辑(英文版)》2001,44(1)

Three synthetic Fe3+ bearing γ-Fe2SiO4 were analyzed usingelectron probe method, and the Mssbauer 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 γ-Fe2SiO4 were interpreted by using the next nearest neighbor effects.  相似文献   

Interaction of adakitic melt-peridotite: Implications for the high-Mg# signature of Mesozoic adakitic rocks in the eastern North China Craton     

Wenliang Xu  Janet M. Hergt  Shan Gao  Fuping Pei  Wei Wang  Debin Yang 《Earth and Planetary Science Letters》2008,265(1-2):123-137

Abundant dunite and harzbugite xenoliths are preserved in Early Cretaceous high-Mg# [63–67, where Mg# = molar 100 × Mg/(Mg + Fe_tot)] diorite intrusions from western Shandong in the North China Craton (NCC). Dunite and some harzburgite xenoliths typically preserve areas of orthopyroxenite (sometimes accompanied by phlogopite) either as veins or as zones surrounding chromite grains. Harzburgite is chiefly composed of olivine, orthopyroxene, minor clinopyroxene and chromian-spinel. High Mg#'s (averaging 91.4) and depletions in Al₂O₃ and CaO (averaging 0.52 wt.% and 0.29 wt.%, respectively) in harzburgite and dunite xenoliths suggest that they are residues formed by large degrees of polybaric melting. However, olivines and orthopyroxenes from dunite xenoliths spatially associated with orthopyroxenite display lower Mg#'s (i.e., 82–87 and 83–89, respectively), suggesting that an adakitic melt–peridotite reaction has taken place. This is consistent with the production of veined orthopyroxene or orthopyroxene + phlogopite in dunite and some harzburgite xenoliths in response to the introduction of adakitic melt into the previously depleted lithospheric mantle (i.e., harzburgite and dunite xenoliths). The presence of orthopyroxene in veins or as a zones surrounding chromite in peridotite xenoliths is thought to be representative of adakitic melt metasomatism. The dunite and harzbugite xenoliths are relatively rich in light rare earth elements (LREEs) and large ion lithophile elements (LILEs), poor in heavy rare earth elements (HREEs) and high field strength elements (HFSEs), and lack Eu anomalies on chondrite normalized trace element diagrams. The initial ⁸⁷Sr/⁸⁶Sr ratios and εNd(t) values for the xenoliths range from 0.7058 to 0.7212 and + 0.18 to ? 19.59, respectively. Taken together, these features, combined with the strong depletion in HFSE and the existence of Archean inherited zircons in the host rocks, suggest that the adakitic melt was derived from the partial melting of early Mesozoic delaminated lower continental crust. The interaction of the adakitic melt with peridotite is responsible for the high-Mg# character of the early Cretaceous diorites in western Shandong.  相似文献   

Low-degree melting of a metasomatized lithospheric mantle for the origin of Cenozoic Yulong monzogranite-porphyry,east Tibet: Geochemical and Sr–Nd–Pb–Hf isotopic constraints     

《Earth and Planetary Science Letters》2006,241(3-4):617-633

SHRIMP zircon U–Pb dating, mineral chemical, element geochemical and Sr–Nd–Pb–Hf isotopic data have been determined for the Yulong monzogranite-porphyry in the eastern Tibet, China. The Yulong porphyry was emplaced into Triassic strata at about 39 Ma. The rocks are weakly peraluminous and show shoshonitic affinity, i.e., alkalis-rich, high K₂O contents with high K₂O / Na₂O ratios, enrichment in LREE and LILE. They also show some affinities with the adakite, e.g., high SiO₂ and Al₂O₃, and low MgO contents, depleted in Y and Yb, and enrichment in Sr with high Sr / Y and La / Yb ratios, and no Eu anomalies. The Yulong porphyry has radiogenic ⁸⁷Sr / ⁸⁶Sr (0.7063–0.7070) and unradiogenic ¹⁴³Nd / ¹⁴⁴Nd (ε_Nd = − 2.0 to − 3.0) ratios. The Pb isotopic compositions of feldspar phenocrysts separated from the Yulong porphyry show a narrow range of ²⁰⁶Pb / ²⁰⁴Pb ratios (18.71–18.82) and unusually radiogenic ²⁰⁷Pb / ²⁰⁴Pb (15.65–15.67) and ²⁰⁸Pb / ²⁰⁴Pb (38.87–39.00) ratios. In situ Hf isotopic composition of zircons that have been SHRIMP U–Pb dated is characterized by clearly positive initial ε_Hf values, ranging from + 3.1 to + 5.9, most between + 4 and + 5. Phenocryst clinopyroxene geothermometry of the Yulong porphyry indicates that the primary magmas had anomalously high temperature (> 1200 °C). The source depth for the Yulong porphyry is at least 100 km inferred by the metasomatic volatile phase (phlogopite–carbonate) relations. Detailed geochemical and Sr–Nd–Pb–Hf isotopic compositions not only rule out fractional crystallization or assimilation-fractional crystallization processes, but also deny the possibility of partial melting of subducted oceanic crust or basaltic lower crust. Instead, low degree (1–5%) partial melting of a metasomatized lithosphere (phlogopite–garnet clinopyroxenite) is compatible with the data. This example gives a case study that granite can be derived directly by partial melting of an enriched lithospheric mantle, which is important to understand the source and origin of diverse granites.  相似文献   

Critical phenomena in thermal conductivity: Implications for lower mantle dynamics     

《Journal of Geodynamics》2008,45(3-5):186-199

Microscopic mechanisms for heat transport in dense minerals (phonon scattering and photon attenuation) exhibit aspects of threshold behavior, discussed qualitatively here. For all minerals examined so-far using laser-flash analysis, the lattice component of the thermal conductivity of the mantle asymptotes to a constant above a critical temperature of ∼1500 K. Radiative transfer calculated from absorption spectra has thresholds in both grain-size and Fe content, and a rather complex dependence on temperature. These critical phenomena impact convection of the lower mantle, because the lattice contribution tends to destabilize the cold boundary layers, whereas radiative transfer mostly promotes stability in the lower mantle, unless the grains are large and Fe-rich, which makes convection chaotic and time-dependent. The specific behavior suggests that flow in the lower mantle is sluggish, whereas flow in the upper mantle-transition zone is time-dependent. The decrease in k_rad as Fe/(Fe + Mg) increases beyond ∼0.1 may be connected with formation of lower mantle, thermo-chemical plumes through positive feedback.  相似文献