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1.
Stephen Mackwell Misha Bystricky Caroline Sproni 《Physics and Chemistry of Minerals》2005,32(5-6):418-425
We have performed a series of interdiffusion experiments on magnesiowüstite samples at room pressure, temperatures from 1,320° to 1,400°C, and oxygen fugacities from 10?1.0 Pa to 10?4.3 Pa, using mixed CO/CO2 or H2/CO2 gases. The interdiffusion couples were composed of a single-crystal of MgO lightly pressed against a single-crystal of (Mg1-x Fe x )1-δO with 0.07<x<0.27. The interdiffusion coefficient was calculated using the Boltzmann–Matano analysis as a function of iron content, oxygen fugacity, temperature, and water fugacity. For the entire range of conditions tested and for compositions with 0.01<x<0.27, the interdiffusion coefficient varies as $$\tilde D\, =\,2.9\times10^{ - 6}\,f_{{\text{O}}_2 }^{0.19}\,x^{0.73}\,{\text{e}}^{ - (209,000\, -\,96,000\,x)/RT}\,\,{\text{m}}^{\text{2}} {\text{s}}^{ -1} $$ These dependencies on oxygen fugacity and composition are reasonably consistent with interdiffusion mediated by unassociated cation vacancies. For the limited range of water activity that could be investigated using mixed gases at room pressure, no effect of water on interdiffusion could be observed. The dependence of the interdiffusion coefficient on iron content decreased with increasing iron concentration at constant oxygen fugacity and temperature. There is a close agreement between our activation energy for interdiffusion extrapolated to zero iron content (x=0) and that of previous researchers who used electrical conductivity experiments to determine vacancy diffusivities in lightly doped MgO. 相似文献
2.
三价铁水解是铁地球化学循环中的一个重要过程,在一定程度上控制了铁在水体中的运移和再分配。实验研究了Fe(Ⅲ)在20℃和46℃水解生成沉淀过程中,上清液的存在形态以及该过程导致的Fe同位素分馏。20℃水解实验有两个时间长度,分别是95天和130天,水解实验结束时上清液中的Fe(Ⅲ)主要以胶体形式存在。不同的水解时间导致的Fe同位素分馏在误差范围内是一致的。20℃水解实验结束时上清液和沉淀之间56Fe/54Fe的同位素组成之间的差异Δ56FeFe(Ⅲ)sup-Fe(Ⅲ)pre为1.15‰;46℃水解实验的时间长度为95天,结束时上清液中的Fe(Ⅲ)主要以离子形式存在,46℃水解实验结束时Δ56FeFe(Ⅲ)sup-Fe(Ⅲ)pre为1.37‰。通过瑞利分馏的公式计算出20℃和46℃时Fe(Ⅲ)水解过程中沉淀和上清液间的瞬时平衡分馏系数分别为0.999 121和0.999 260。 相似文献
3.
Fe是海洋“生物泵”中限制浮游生物生长和控制海洋初级生产力的主要因素之一,也可间接影响大气中CO2含量,反馈于全球的气候变化。近年来基于多接收电感耦合等离子体质谱仪(MC ICP MS)分析方法的改进及测试精度的提高,应用Fe同位素组成、变化及其分馏机制,为研究海水中Fe的主要来源以及示踪海洋环境中Fe的循环过程等,提供了一个有效地球化学指标,也对示踪地球不同演化阶段的海洋沉积环境变化具有指示意义。较为详细地介绍了海洋环境中不同储库的Fe同位素组成,洋中脊热液流体—玄武岩、海水—大洋玄武岩等水—岩反应影响Fe同位素分馏效应的主要因素及地球不同演化阶段古海洋沉积环境中的Fe同位素变化。认为海洋环境下Fe同位素可以产生较为明显的分馏作用,轻铁同位素具有更易活动、易迁移的特征,并进一步提出不同相态、不同矿物间Fe同位素分馏系数的确定等相关问题仍是今后Fe同位素研究的主要方向。 相似文献
4.
Fe同位素的MC-ICP-MS测试方法 总被引：4，自引：0，他引：4
过渡族元素同位素研究是新兴的研究领域和国际研究前沿, 是同位素地球化学研究的热点。本研究利用Neptune型多接收等离子质谱(MC-ICP-MS), 采用标准-样品-标准交叉校正和以Cu为内标的方法对仪器的质量歧视进行校正, 对浓度效应、基质效应、干扰元素扣除和测试的长期重现性进行了检验, 建立了高精度的Fe同位素测试技术。这两种校正方法对实验室标准HSP I Fe在一段时间内δ56Fe和δ57Fe的测试结果分别为0.08‰(2SD)和0.14‰(2SD)分析精度达到国际同类实验室水平, 测试结果在误差范围内与文献值完全一致。 相似文献
5.
低温绿泥石成分温度计Fe/(Fe+Mg)校正的必要性问题 总被引：1，自引：0，他引：1
绿泥石是沉积岩、低级变质岩和水热蚀变岩中的常见矿物,基于四次配位Al含量的绿泥石成分温度计是确定古成岩或变质温度的最主要的手段之一。介绍了四种应用最为广泛的绿泥石成分温度计的原理,并从离子替代规律和比较研究的角度着重讨论了近年来关于绿泥石成分温度计校正的必要性。研究表明,在铝饱和的条件下,根据绿泥石中的Fe/(Fe Mg)值对绿泥石温度计进行校正并不能使计算值与实际值更为接近,而且从晶体化学的角度看,全岩的Fe/(Fe Mg)主要影响的是绿泥石中六次配位Fe与Mg的占位,而且偶合置换(Si4 )Ⅳ(Mg2 )Ⅵ—(Al3 )Ⅳ(Al3 )Ⅵ和(Si4 )Ⅳ(Fe2 )Ⅵ—(Al3 )Ⅳ(Al3 )Ⅵ共同控制着四次配位Al的占位。所以在铝饱和的岩石体系中可不必进行Fe/(Fe Mg)值的校正。 相似文献
6.
通过实验建立了野外水质Fe2 、Fe3 的测定方法,不用电力和携带仪器设备,目视比色。简便快速,具有较好的准确度。 相似文献
7.
L. P. Ogorodova I. A. Kiseleva M. F. Vigasina L. V. Mel’chakova D. A. Ksenofontov I. A. Bryzgalov 《Geochemistry International》2017,55(7):669-673
The paper presents data on the thermochemical study (high-temperature melt calorimetry in a Tian–Calvet microcalorometer) of two natural Mg–Fe amphiboles: anthophyllite Mg2.0(Mg4.8Fe0.2 2+)[Si8.0O22](OH)2 from Kukh-i-Lal, southwestern Pamirs, Tajikistan, and gedrite Na0.4Mg2.0(Mg1.7Fe0.2 2+Al1.3)[Si6.3Al1.7O22](OH)2 from the Kola Peninsula, Russia. The enthalpy of formation from elements is obtained as–12021 ± 20 kJ/mol for anthophyllite and as–11545 ± 12 kJ/mol for gedrite. The standard entropy, enthalpy, and Gibbs energy of formation are evaluated for Mg–Fe amphiboles of theoretical composition. 相似文献
8.
《吉林大学学报(地球科学版)》2015,(Z1)
<正>氧化铁作为高活性矿物的重要内因是以变价元素铁构成的氧化铁循环过程活跃。土壤铁循环是一个特殊微生物驱动的生物地球化学过程,长期以来普遍认为,以氧化铁矿物为末端电子受体、铁还原菌通过氧化电子供体藕联的氧化铁异化还原过程[1],与以游离态Fe(II)为电子受体、铁氧化菌作用产生的Fe(II)微生物氧化成矿过程[2],组成了完整的铁循环链[3](图1过程I和II)。1980年底有研究发现,厌氧条件下游离态 相似文献
9.
11.
L. P. Ogorodova L. V. Mel’chakova M. F. Vigasina I. A. Kiseleva I. A. Bryzgalov 《Geochemistry International》2017,55(3):257-262
The thermochemical study of two natural trioctahedral Mg–Fe chlorites—clinochlores was carried out using high-temperature melt solution calorimetry with a Tian–Calvet microcalorimeter. The enthalpies of formation of clinochlores of compositions (Mg4.9Fe 0.3 2+ Al0.8)[Si3.2Al0.8O10](OH)8 (–8811 ± 12 kJ/mol) and (Mg4.3Fe 0.7 2+ Al1.0)[Si3.0Al1.0O10](OH)8 (–8696 ± 13 kJ/mol) from elements were determined. The values of the standard entropies and the Gibbs energies of formation of the studied natural minerals as well as thermodynamic properties of Mg–Fe chlorites of theoretical composition were estimated. 相似文献
12.
P. A. van Aken V. J. Styrsa B. Liebscher A. B. Woodland G. J. Redhammer 《Physics and Chemistry of Minerals》1999,26(7):584-590
The Fe M
2,3-edge spectra of solid solutions of garnets (almandine-skiagite Fe3(Al1–xFex)2[SiO4]3 and andradite-skiagite (Fe1–xCax)3Fe2[SiO4]3), pyroxenes (acmite-hedenbergite (Ca1–xNax)(Fe2+
1−xFe3+
x)Si2O6), and spinels (magnetite-hercynite Fe(Al1–xFex)2O4) have been measured using the technique of parallel electron energy-loss spectroscopy (EELS) conducted in a transmission
electron microscope (TEM). The Fe M
2,3 electron energy-loss near-edge structures (ELNES) of the minerals exhibit a characteristic peak located at 4.2 eV and 2.2 eV
for trivalent and divalent iron, respectively, prior to the main maximum at about 57 eV. The intensity and energy of the pre-edge
feature varies depending on Fe3+/ΣFe. We demonstrate a new quantitative method to extract the ferrous/ferric ratio in minerals. A systematic relationship
between Fe3+/ΣFe and the integral intensity ratio of the main maximum and the pre-edge peak of the Fe M
2,3 edge is observed. Since the partial cross sections of the Fe M
2,3 edges are some orders of magnitude higher than those of the Fe L
2,3 edges, the Fe M
2,3 edges are interesting for valence-specific imaging of Fe. The possibility of iron valence-specific imaging is illustrated
by Fe M
2,3-ELNES investigations with high lateral resolution from a sample of ilmenite containing hematite exsolution lamellae that
shows different edge shapes consistent with variations in the Fe3+/ΣFe ratio over distances on the order of 100 nm.
Received: 14 April 1998 / Revised, accepted: 8 March 1999 相似文献
13.
T. Müller R. Dohmen H. W. Becker Jan H. ter Heege S. Chakraborty 《Contributions to Mineralogy and Petrology》2013,166(6):1563-1576
Chemical interdiffusion of Fe–Mg along the c-axis [001] in natural diopside crystals (X Di = 0.93) was experimentally studied at ambient pressure, at temperatures ranging from 800 to 1,200 °C and oxygen fugacities from 10?11 to 10?17 bar. Diffusion couples were prepared by ablating an olivine (X Fo = 0.3) target to deposit a thin film (20–100 nm) onto a polished surface of a natural, oriented diopside crystal using the pulsed laser deposition technique. After diffusion anneals, compositional depth profiles at the near surface region (~400 nm) were measured using Rutherford backscattering spectroscopy. In the experimental temperature and compositional range, no strong dependence of D Fe–Mg on composition of clinopyroxene (Fe/Mg ratio between Di93–Di65) or oxygen fugacity could be detected within the resolution of the study. The lack of fO2-dependence may be related to the relatively high Al content of the crystals used in this study. Diffusion coefficients, D Fe–Mg, can be described by a single Arrhenius relation with $$D^{{{\text{Fe}} - {\text{Mg}}}} = 2. 7 7\pm 4. 2 7\times 10^{ - 7} {\text{exp(}}-3 20. 7\pm 1 6.0{\text{ kJ}}/{\text{mol}}/{\text{RT)m}}^{ 2} /{\text{s}}.$$ D Fe–Mg in clinopyroxene appears to be faster than diffusion involving Ca-species (e.g., D Ca–Mg) while it is slower than D Fe–Mg in other common mafic minerals (spinel, olivine, garnet, and orthopyroxene). As a consequence, diffusion in clinopyroxene may be the rate-limiting process for the freezing of many geothermometers, and compositional zoning in clinopyroxene may preserve records of a higher (compared to that preserved in other coexisting mafic minerals) temperature segment of the thermal history of a rock. In the absence of pervasive recrystallization, clinopyroxene grains will retain compositions from peak temperatures at their cores in most geological and planetary settings where peak temperatures did not exceed ~1,100 °C (e.g., resetting may be expected in slowly cooled mantle rocks, many plutonic mafic rocks, or ultra-high temperature metamorphic rocks). 相似文献
14.
15.
《吉林大学学报(地球科学版)》2015,(Z1)
<正>高硅花岗岩(w(Si O2)72%)的Fe同位素组成相对低硅样品显著偏重,其成因被解释为流体出溶[1-2]、Soret扩散[3]或分离结晶[4-5]。高硅花岗岩中,由于铁镁质矿物含量极低,全岩Fe含量相当一部分赋存于长石中,显著不同于低硅花岗岩,后者的Fe几乎都存在于铁镁质矿物和磁铁矿中。这一Fe赋存状态的改变对高硅花岗岩铁同位素组成的影响尚属未知。本研究测试了大别造山带I型花岗岩中长石和其他共存矿物 相似文献
16.
Fe3+纳米胶体颗粒的光吸收边蓝移与溶液中Al/Fe比的关系 总被引：4，自引：2，他引：2
合成了n（Al）／n（Fe）和碱化度不同的45个聚合氯化铝铁（PAFC）样品,进行了光谱分析,结果显示光吸收边蓝移或红移以及Fe（Ⅲ）羟基氧化物和Al-Fe共聚体纳米胶体颗粒大小分布与溶液的Al／Fe比和碱化度（B=[OH]／[Al＋Fe]）密切相关。电镜观察和电子衍射分析表明：Al（Ⅲ）的加入使Fe（Ⅲ）羟基氧化物和Al-Fe共聚体纳米胶体颗粒变小、有序度降低是造成PAFE光吸收边蓝移和保持胶体颗粒在亚稳定状态下存在的重要原因。当n（Al）／n（Fe）〉8：2后,PAFC溶液中Fe（Ⅲ）羟基氧化物和Al-Fe共聚体胶体主要以〈10m的纳米颗粒形态存在,对应的光谱能级提高到26000cm^-1以上,且各种曰值下Fe^3＋的光谱能级趋于一致。这表明,在大量Al（Ⅲ）存在条件下,PAFE中Fe3^＋的所处的化学环境相似。点能谱分析显示,n（Al）／n（Fe）=4：6的样品中颗粒物的化学计量比最接近AlOOH,FeOOH,溶液的稳定性最差。 相似文献
17.
S. Rossano E. Balan G. Morin J.-P. Bauer G. Calas C. Brouder 《Physics and Chemistry of Minerals》1999,26(6):530-538
Tektite glasses are investigated using 57Fe Mössbauer spectroscopy. Room temperature spectra analysis is performed using two complementary analytical methods based on two-dimensional distributions of both isomer shift and quadrupole splitting. No a priori correlation between the two hyperfine parameters is considered. The first method, based on a shape independent distribution, provides the justification for the Gaussian distribution shape used in the second method. No ferric iron contribution is evidenced by Mössbauer spectra analysis in these samples, although several criteria are used. Ferrous iron sites are shown to be continuously distributed between four- and five-fold co-ordinated sites. 相似文献
18.
Soma Kuwabara Hidenori Terasaki Keisuke Nishida Yuta Shimoyama Yusaku Takubo Yuji Higo Yuki Shibazaki Satoru Urakawa Kentaro Uesugi Akihisa Takeuchi Tadashi Kondo 《Physics and Chemistry of Minerals》2016,43(3):229-236
The sound velocity (V P) of liquid Fe–10 wt% Ni and Fe–10 wt% Ni–4 wt% C up to 6.6 GPa was studied using the ultrasonic pulse-echo method combined with synchrotron X-ray techniques. The obtained V P of liquid Fe–Ni is insensitive to temperature, whereas that of liquid Fe–Ni–C tends to decrease with increasing temperature. The V P values of both liquid Fe–Ni and Fe–Ni–C increase with pressure. Alloying with 10 wt% of Ni slightly reduces the V P of liquid Fe, whereas alloying with C is likely to increase the V P. However, a difference in V P between liquid Fe–Ni and Fe–Ni–C becomes to be smaller at higher temperature. By fitting the measured V P data with the Murnaghan equation of state, the adiabatic bulk modulus (K S0) and its pressure derivative (K S ′ ) were obtained to be K S0 = 103 GPa and K S ′ = 5.7 for liquid Fe–Ni and K S0 = 110 GPa and K S ′ = 7.6 for liquid Fe–Ni–C. The calculated density of liquid Fe–Ni–C using the obtained elastic parameters was consistent with the density values measured directly using the X-ray computed tomography technique. In the relation between the density (ρ) and sound velocity (V P) at 5 GPa (the lunar core condition), it was found that the effect of alloying Fe with Ni was that ρ increased mildly and V P decreased, whereas the effect of C dissolution was to decrease ρ but increase V P. In contrast, alloying with S significantly reduces both ρ and V P. Therefore, the effects of light elements (C and S) and Ni on the ρ and V P of liquid Fe are quite different under the lunar core conditions, providing a clue to constrain the light element in the lunar core by comparing with lunar seismic data. 相似文献
19.
Huan ZHANG Zhaohui JIN Lu HAN Zongming XIU Chenghua QIN 《中国地球化学学报》2006,25(B08):132-133
Degradation of organic halides by reductive dehalogenation promoted by zerovalent metals is a very active research area. The use of nano-sized particles of zero valent iron （ZVI） or bimetallic combinations of ZVI currently attracts the most attention due to their high surface areas and high reactive activity. The introduction of second catalytic metals, such as Pd, Pt, Cu, or Ni, results in an even higher dehalogenation rate. The supported zero-valent iron materials have higher activity and greater flexibility for environmental remediation applications than other forms of ZVI. Nano ZVI supported on micro-scale exfoliated graphite was prepared by using KBH4 as the reducing agent in the H2O/ethanol solution of Fe^2＋ in the laboratory. Then the ethanol solution of Cu^2＋ was added to the fleshly prepared wet supported nano ZVI. The Fe/Cu bimetallic particles supported on the graphite were obtained because of the reduction and deposition of Cu on the Fe surface. The TEM image showed that iron particles were highly dispersed on the surface of graphite. In this study, supported zero valent Cu/Fe bimetallic nanoparticles were used for the dehalogenation of trichloroethylene （TCE） in batch experiments. The dechlorination rate of supported zero valent Fe/Cu bimetallic nanoparticles was greater than the supported nano ZVI. Supported Cu/Fe bimetal with 4 wt% Cu had the fastest dehalogenation rate than that with different content of Cu. When the nana FeO dosage was 5 g/L in the dehalogention system, 8 mg/L of TCE was completely dechlorinated within 4 hours. Increasing or decreasing the FeO dosage, the dechlorination rate could be worse. When the concentration of Fe^2＋ was 0.05 mol/L during the preparation by KBH4 reduction, the nano Cu/Fe particles exhibited the spheral shape with 50-80 nm in size. When the concentration of Fe^2＋ was higher （0.2 mol/L）, the nano particles were the palpus structure and had the poor dehalogenation effect on the TCE. 相似文献
20.
A new thermodynamic model for multi-component spinel solid solutions has been developed which takes into account thermodynamic consequences of cation mixing in spinel sublattices. It has been applied to the evaluation of thermodynamic functions of cation mixing and thermodynamic properties of Fe3O4–FeCr2O4 spinels using intracrystalline cation distribution in magnetite, lattice parameters and activity-composition relations of magnetite–chromite solid solutions. According to the model, cation distribution in binary spinels, (Fe1-x2+ Fex3+)[Fex2+Fe2-2y-x3+Cr2y]O4, and their thermodynamic properties depend strongly on Fe2+–Cr3+ cation mixing. Mixing of Fe2+–Fe3+ and Fe3+–Cr3+ can be accepted as ideal. If Fe2+, Fe3+ and Cr are denoted as 1, 3 and 4 respectively, the equation of cation distribution is –RT ln(x2/((1–x)(2–2y–x)))= G13* + (1–2x)W13+y(W14–W13–W34) where G13* is the difference between the Gibbs energy of inverse and normal magnetite, Wij is a Margules parameter of cation mixing and G13*, J/mol =–23,000+13.4 T, W14=36 kJ/mol, W13=W34=0. The positive nonconfigurational Gibbs energy of mixing is the main reason for changing activity–composition relations with temperature. According to the model, the solvus in Fe3O4–FeCr2O4 spinel has a critical temperature close to 500°C, which is consistent with mineralogical data. 相似文献