活塞圆筒和多面砧高压装置中常用的氧逸度控制和原位监测方法

氧逸度是定量表示一个体系氧化还原能力的指标，反映了体系中氧气的分压或者逃逸能力。在地球科学中，它反映了岩石和矿物中变价元素的氧化还原状态，指示了不同岩石矿物氧化性/还原性的相对强弱。相同岩石矿物不同氧逸度可以导致其物理化学性质发生大的改变，因此在实验地球科学中准确控制并监测高温高压实验条件下的氧逸度具有非常重要的意义。本文从实验技术角度出发，首先介绍了活塞圆筒和多面砧高压装置中利用双胶囊技术在不含水和含水体系中控制氧逸度的方法、原理、装置和注意事项；接着描述了用过渡金属合金固溶体和惰性金属合金作为氧传感器原位测量氧逸度的原理、注意事项和地质应用，然后展示了氧离子固体电解质法控制和监测氧逸度的原理、装置和局限，提出了可能的改进方法。目前由于技术限制，氧逸度在高压实验中的控制和监测方法还不成熟，导致其对矿物和岩石物理化学性质的影响极可能被低估甚至错估。因此积极研究发展并推动高压下氧逸度的控制和监测技术非常重要且必要。     

Oxygen fugacity control in piston-cylinder experiments

The main goal of this study was to develop and test a capsule assembly for use in piston-cylinder experiments where oxygen fugacity could be controlled in the vicinity of the QFM buffer without H₂O loss or carbon contamination of the sample material. The assembly consists of an outer Pt-capsule containing a solid buffer (Ni–NiO or Co–CoO) plus H₂O and an inner AuPd-capsule, containing the sample, H₂O and a Pt-wire. No H₂O loss is observed from the sample, even after 48 h, but a slight increase in H₂O content is found in longer runs due to oxygen and hydrogen diffusion into the AuPd-capsule. Oxygen fugacity of runs in equilibrium with the Ni–NiO (NNO) and Co–CoO (CoCO) buffers was measured by analyzing Fe dissolved in the Pt-wire and in the AuPd-capsule. The second method gives values that are in good agreement with established buffer values, whereas results from the first method are one half to one log units higher than the established values.     

地幔氧逸度的时空变化

地幔氧逸度是反映地幔氧化还原程度的参量,由温度、压力、岩石化学成分、矿物结构等共同作用控制.目前对上地幔氧逸度的研究主要针对镁橄榄石-磁铁矿-石英体系、含角闪石的橄榄岩体系和玄武岩(熔体)体系,通过实验岩石学方法进行.地幔氧逸度在垂直深度上随深度增加而减小受到普遍认可.天然样品和理论研究认为,岩石圈地幔底部的软流圈氧逸...     

C-O-H-S fluid composition and oxygen fugacity in graphitic metapelites

Abstract C-O-H fluid produced by the equilibration of H₂O and excess graphite must maintain the atomic H/O ratio of water, 2:1. This constraint implies that all thermodynamic properties of the fluid are uniquely determined at isobaric-isothermal conditions. The O₂, H₂O and CO₂ fugacities (fo₂, f_H2O and f_CO2) of such fluids have been estimated from equations of state and fit as a function of pressure and temperature. These fugacities can be taken as characteristic for graphitic metamorphic systems in which the dominant fluid source is dehydration, e.g. pelitic lithologies. Because there are no compositional degrees of freedom for graphite-saturated fluids produced entirely by dehydration, the variance of the dehydration process is not increased in comparison with that in non-graphitic systems. Thus, compositional ‘buffering’of C-O-H fluids by dehydration equilibria, a common petrological model, requires that redox reactions, decarbonation reactions or external, H/O ± 2, fluid sources perturb the evolution of the metamorphic system. Such perturbations are not likely to be significant in metapelitic environments, but their tendency will be to increase the f_O2 of the fluid phase. At high metamorphic grades, pyrite desulphidation reactions may cause a substantial reduction of f_H2O and slight increases in f_O2 and f_CO2 relative to sulphur-free fluid. At low metamorphic grade, sulphur solubility in H/O ± 2 fluids is so low that pyrite decomposition must occur by sulphur-conserving reactions that cause iron depletion in silicates, a common feature of sulphidic pelites. With increasing temperature and sulphur solubility, pyrite desulphidation may be driven by dehydration reactions or infiltration of H₂O-rich fluids. The absence of magnetite and the assemblages carbonate + aluminosilicate or pyrite + pyrrhotite + ilmenite from most graphitic metapelites is consistent with an H/O = 2 model for GCOH(S) fluid. For graphitic rocks in which such a model is inapplicable, a phase diagram variable that defines the H/O ratio of GCOH(S) fluid is more useful than the conventional f_O2 variable.     

Oxygen fugacity control in piston-cylinder experiments: a re-evaluation

Jakobsson (Contrib Miner Petrol 164(3):397–407, 2012) investigated a double capsule assembly for use in piston-cylinder experiments that would allow hydrous, high-temperature, and high-pressure experiments to be conducted under controlled oxygen fugacity conditions. Using a platinum outer capsule containing a metal oxide oxygen buffer (Ni–NiO or Co–CoO) and H₂O, with an inner gold–palladium capsule containing hydrous melt, this study was able to compare the oxygen fugacity imposed by the outer capsule oxygen buffer with an oxygen fugacity estimated by the AuPdFe ternary system calibrated by Barr and Grove (Contrib Miner Petrol 160(5):631–643, 2010). H₂O loss or gain, as well as iron loss to the capsule walls and carbon contamination, is often observed in piston-cylinder experiments and often go unexplained. Only a few have attempted to actually quantify various aspects of these changes (Brooker et al. in Am Miner 83(9–10):985–994, 1998; Truckenbrodt and Johannes in Am Miner 84:1333–1335, 1999). It was one of the goals of Jakobsson (Contrib Miner Petrol 164(3):397–407, 2012) to address these issues by using and testing the AuPdFe solution model of Barr and Grove (Contrib Miner Petrol 160(5):631–643, 2010), as well as to constrain the oxygen fugacity of the inner capsule. The oxygen fugacities of the analyzed melts were assumed to be equal to those of the solid Ni–NiO and Co–CoO buffers, which is incorrect since the melts are all undersaturated in H₂O and the oxygen fugacities should therefore be lower than that of the buffer by 2 log $a_{{{\text{H}}_{ 2} {\text{O}}}}$ .     

The magmatic oxygen fugacity of an ultrabasic dyke

The magmatic oxygen fugacity (fO₂) of a thirty foot wide feldspathic peridotite dyke has been determined using the experimental method of Fudali (1965). Determinations were made on samples from both the marginal and central portions of the dyke and a difference of approximately one order of magnitude in fO₂ was observed. This difference is attributed to the increase in the H₂O content of the liquid as crystallization proceeded and to diffusion of hydrogen out of the dyke. It is concluded that the dyke was emplaced with an fO₂ between 10^–8 and 10^–9 atmospheres. Data on the absorbtion of Fe by the silver/palladium sample containers during the experiments are given in an appendix.     

中酸性侵入岩的氧逸度计算

氧逸度是岩石物理化学的1个重要参数,对岩浆演化、岩石成因和岩浆热液成矿具有明显的控制作用。含有变价元素的矿物常被用来计算成岩与成矿过程中的氧逸度,但是不同方法之间的对比研究较少,各种方法的适用性还不明晰。作者对晋东北黑狗背花岗岩体的氧逸度进行了较为系统的研究,通过黑云母、角闪石、磁铁矿-钛铁矿矿物对和锆石的Ce异常的氧逸度计算,发现不同方法的估算结果存在较大的差异,甚至会得出完全相左的结论。其中,基于Fe~(3+)/Fe~(2+)比值的黑云母和磁铁矿-钛铁矿氧逸度计计算结果吻合度较高,可适用于中酸性侵入岩的氧逸度研究,而基于Fe/(Fe+Mg)比值的氧逸度计算方法可能受到母岩浆化学成分的影响,不适合应用于低镁侵入岩的氧逸度估算。     

Composition of olivine,silica activity and oxygen fugacity in kimberlite

Two generations of primary olivine are present in kimberlite, rounded phenocrysts (Fo₉₄Fo₉₁) and euhedral groundmass olivines (Fo₉₁Fo_88-5). Rounded phenocrysts less magnesian than Fo₈₈ are considered to be mantle derived xenocrysts; such crystals comprise up to 40% of the phenocrysts material in kimberlite. Calculated silica activity ranges from 10^?1,5 at 1200 °C, 50 kbs, to between 10^?1,6 and 10^?2.4 at 600 °C, 0.5–1.0 kb. Silica buffers involving olivines, pyroxenes and garnet are considered. Oxygen fugacities on the order of 10^?20 bars indicate that kimberlite magmas are highly reduced at the time of groundmass formation.     

The effect of oxygen fugacity on ionic conductivity in olivine

The oxygen fugacity(f_O2) may affect the ionic conductivity of olivine under upper mantle conditions because Mg vacancies can be produced in the crystal structure by the oxidization of iron from Fe²⁺ to Fe3+. Here we investigated olivine ionic conductivity at 4 GPa, as a function of temperature, crystallographic orientation, and oxygen fugacity, corresponding to the topmost asthenospheric conditions. The results demonstrate that the ionic conductivity is insensitive to f_O2 under relatively reduced conditions(f_O2 below Re-ReO₂ buffer), whereas it has a clear f_O2-dependence under relatively oxidized conditions(f_O2 around the magnetite-hematite buffer). The ionic conduction in olivine may contribute significantly to the conductivity anomaly in the topmost asthenosphere especially at relatively oxidized conditions.     

Armalcolite stability as a function of pressure and oxygen fugacity

The stability of synthetic armalcolite of composition (Fe_0.5Mg_0.5Ti₂O₅ was studied as a function of total pressure up to 15 kbar and 1200°C and also as a function of oxygen fugacity (?O₂) at 1200°C and 1 atm total pressure. The high pressure experiments were carried out in a piston-cylinder apparatus using silver-palladium containers. At 1200°C, armalcolite is stable as a single phase at 10 kbar. With increasing pressure, it breaks down ($\text{dT}\text{dP}\text{= 20°C/}\text{kbar}$), to rutile, a more magnesian armalcolite, and ilmenite solid solution. At 14 kbar, this three-phase assemblage gives way ($\text{dT}\text{dP}\text{= 30°C/}\text{kbar}$) to a two-phase assemblage of rutile plus ilmenite solid solution.A zirconian-armalcolite was synthesized and analyzed; 4 wt % ZrO₂ appears to saturate armalcolite at 1200°C and 1 atm. The breakdown of Zr-armalcolite occurs at pressures of 1–2 kbar less than those required for the breakdown of Zr-free armalcolite. The zirconium partitions approximately equally between rutile and ilmenite phases.The stability of armalcolite as a function of ?O₂ was determined thermogravimetrically at 1200°C and 1 atm by weighing sintered pellets in a controlled atmosphere furnace. Armalcolite, (Fe_0.5Mg_0.5)-Ti₂O₅, is stable over a range ?O₂ from about 10^?9.5to 10^?10.5 atm. Below this range to at least 10^?12.8 atm, ilmenite plus a reduced armalcolite are formed. These products were observed optically and by Mössbauer spectroscopy, and no metallic iron was detected; therefore, some of the titanium must have been reduced to Ti³⁺. This reduction may provide yet another mechanism to explain the common association of ilmenite rims around lunar armalcolites.     

Hydration of mantle olivine under variable water and oxygen fugacity conditions

The incorporation of H into olivine is influenced by a significant number of thermodynamic variables (pressure, temperature, oxygen fugacity, etc.). Given the strong influence that H has on the solidus temperature and rheological behavior of mantle peridotite, it is necessary to determine its solubility in olivine over the range of conditions found in the upper mantle. This study presents results from hydration experiments carried out to determine the effects of pressure, temperature, and the fugacities of H₂O and O₂ on H solubility in San Carlos olivine at upper mantle conditions. Experiments were carried out at 1–2 GPa and 1,200 °C using a piston-cylinder device. The fugacity of O₂ was controlled at the Fe⁰–FeO, FeO–Fe₃O₄, or Ni⁰–NiO buffer. Variable duration experiments indicate that equilibration is achieved within 6 h. Hydrogen contents of the experimental products were measured by secondary ion mass spectrometry, and relative changes to the point defect populations were investigated using Fourier transform infrared spectroscopy. Results from our experiments demonstrate that H solubility in San Carlos olivine is sensitive to pressure, the activity of SiO₂, and the fugacities of H₂O and O₂. Of these variables, the fugacity of H₂O has the strongest influence. The solubility of H in olivine increases with increasing SiO₂ activity, indicating incorporation into vacancies on octahedral lattice sites. The forsterite content of the olivine has no discernible effect on H solubility between 88.17 and 91.41, and there is no correlation between the concentrations of Ti and H. Further, in all but one of our experimentally hydrated olivines, the concentration of Ti is too low for H to be incorporated dominantly as a Ti-clinohumite-like defect. Our experimentally hydrated olivines are characterized by strong infrared absorption peaks at wavenumbers of 3,330, 3,356, 3,525, and 3,572 cm^?1. The heights of peaks at 3,330 and 3,356 cm^?1 correlate positively with O₂ fugacity, while those at 3,525 and 3,572 cm^?1 correlate with H₂O fugacity.     

The role of fluorine and oxygen fugacity in the genesis of the ultrapotassic rocks

The effects of H₂O, CO₂, CH₄ and HF on partial melting of a model phlogopite harzburgite mantle are considered with regard to the production of ultrapotassic magmas. Fluorine has a polymerising effect in H₂O-poor conditions, but in the presence of abundant H₂O where HF rather than F is dominant, the overall effect is depolymerisation. Methane also dissolves by forming (OH)^– groups, and so has a depolymerising effect. Group I ultrapotassic rocks (lamproites) probably originate from primary magmas with SiO₂ contents ranging from around 40 wt% to at least 52 wt%. This range can be explained by differing depths of origin from a similar source with a similar reduced H₂O-CH₄-HF volatile mixture. The formation of silica-rich initial melts from a model phlogopite harzburgite is assisted by the presence of CH₄ and HF. Dissociation of less than 0.1 wt% H₂O, driven by H₂ loss, is sufficient to cause oxidation during emplacement to observed oxidation states. Silica-poor ultrapotassic rocks could be produced at higher pressures in a reduced environment, or in an oxidised environment with high CO₂/(CO₂ + H₂O) ratios.Group II (African Rift) potassic rocks may originate in H₂O-poor conditions in which fluorine will maintain a large phlogopite phase field, so that initial melts will be magnesian and silica-undersaturated.     

The oxidation state of europium as an indicator of oxygen fugacity

The distribution of Eu between plagioclase feldspar and magmatic liquid has been determined experimentally for basaltic and andesitic systems as a function of temperature and oxygen fugacity at one atmosphere total pressure. Using the approach of Philpotts the ratios $\text{Eu}{}^{\mathrm{2+}}\text{Eu}{}^{\mathrm{3+}}$ in plagioclase and coexisting magmatic liquid have been calculated. These ratios appear to be simply related to oxygen fugacity for the bulk compositions studied here. Using published trace element distribution data for natural rocks oxygen fugacities may be calculated from these experimental results. For terrestrial basalts calculated oxygen fugacities average 10^?7 with little dispersion from this value. Andesites average 10^?8.1 with considerable dispersion, while dacites and rhyodacites average 10^?9.1, also with considerable dispersion. Oxygen fugacities for lunar ferrobasalts cluster tightly around 10^?12.7. Data on achondritic meteorites are limited, but calculations indicate oxygen fugacities of two-to-five orders of magnitude lower than lunar ferrobasalts.     

兴蒙造山带北部岩石圈地幔橄榄岩氧逸度特征研究

在大兴安岭北部的诺敏和科洛地区的新生代玄武岩中发现了尖晶石相的橄榄岩包体.地幔橄榄岩中橄榄石的Mg#说明了研究区上地幔具有部分难熔的特点.在橄榄石含量与Fo图解中,有一部分橄榄岩包体落在太古代和元古代的地幔区域,揭示了研究区的岩石圈地幔存在古老岩石圈地幔的残余.研究区方辉橄榄岩与二辉橄榄岩有显示高氧逸度值,FMQ+1....     

Frequency dependent electrical properties of dunite as functions of temperature and oxygen fugacity

Using impedance spectroscopy, we have measured the electrical properties of two dunites and a single crystal olivine sample from 1000 to 1200° C as a function of oxygen fugacity (f _{o 2}). Two conduction mechanisms with resistances that add in series are observed for the dunites corresponding to grain interior and grain boundary conduction mechanisms. The conductivities for each mechanism were determined by analyzing the data using a complex nonlinear least squares fitting routine and the equivalent circuit approach. The grain interiors display a conductivity dependent on f _{o 2} to the 1/5.5–1/7 power, consistent with other determinations, and interpreted as indicating small polaron transport (Fe _Mg ^· ). The grain boundaries demonstrate a weaker f _{o 2} dependence that is dependent on temperature and material. Under certain conditions the f _{o 2} dependence of the grain boundary conductivity is negative. This result indicates that oxygen ion transport is probably not the dominant grain boundary charge transport mechanism; however, an unequivocal determination of the grain boundary mechanism has not been achieved. In some dunites the grain boundaries are more conductive than the grain interiors; in other dunites they are more resistive than grain interiors. The grain boundaries do not enhance the total conductivity of any of the materials of this study but are the controlling mechanism in some instances. Measurement of the complex electrical response at frequencies as low as 10^-4 Hz is required to determine the role of grain boundaries on the overall electrical properties of polycrystalline dunite.     

Nitrogen solubility in basaltic melt. Part I. Effect of oxygen fugacity

The role of the oxygen fugacity on the incorporation of nitrogen in basaltic magmas has been investigated using one atmosphere high temperature equilibration of tholeiitic-like compositions under controlled nitrogen and oxygen partial pressures in the [C-N-O] system. Nitrogen was extracted with a CO₂ laser under high vacuum and analyzed by static mass spectrometry. Over a redox range of 18 oxygen fugacity log units, this study shows that the incorporation of nitrogen in silicate melts follows two different behaviors. For log fO₂ values between −0.7 and −10.7 (the latter corresponding to IW − 1.3), nitrogen dissolves as a N₂ molecule into cavities of the silicate network (physical solubility). Nitrogen presents a constant solubility (Henry’s) coefficient of 2.21 ± 0.53 × 10⁻⁹ mol g⁻¹ atm⁻¹ at 1425°C, identical within uncertainties to the solubility of argon. Further decrease in the oxygen fugacity (log fO₂ between −10.7 and −18 corresponding to the range from IW − 1.3 to IW − 8.3) results in a drastic increase of the solubility of nitrogen by up to 5 orders of magnitude as nitrogen becomes chemically bounded with atoms of the silicate melt network (chemical solubility). The present results strongly suggest that under reducing conditions nitrogen dissolves in silicate melts as N³⁻ species rather than as CN⁻ cyanide radicals. The nitrogen content of a tholeiitic magma equilibrated with N₂ is computed from thermochemical processing of our data set as

     

Metal-silicate partitioning and constraints on core composition and oxygen fugacity during Earth accretion

We present the results of new partitioning experiments between metal and silicate melts for a series of elements normally regarded as refractory lithophile and moderately siderophile and volatile. These include Si, Ti, Ni, Cr, Mn, Ga, Nb, Ta, Cu and Zn. Our new data obtained at 3.6 and 7.7 GPa and between 2123 and 2473 K are combined with literature data to parameterize the individual effects of oxygen fugacity, temperature, pressure and composition on partitioning. We find that Ni, Cu and Zn become less siderophile with increasing temperature. In contrast, Mn, Cr, Si, Ta, Nb, Ga and Ti become more siderophile with increasing temperature, with the highly charged cations (Nb, Ta, Si and Ti) being the most sensitive to variations of temperature. We also find that Ni, Cr, Nb, Ta and Ga become less siderophile with increasing pressure, while Mn becomes more siderophile with increasing pressure. Pressure effects on the partitioning of Si, Ti, Cu and Zn appear to be negligible, as are the effects of silicate melt composition on the partitioning of divalent cations. From the derived parameterization, we predict that the silicate Earth abundances of the elements mentioned above are best explained if core formation in a magma ocean took place under increasing conditions of oxygen fugacity, starting from moderately reduced conditions and finishing at the current mantle-core equilibrium value.     

A redox profile of the Slave mantle and oxygen fugacity control in the cratonic mantle

The authors report a redox profile based on Mössbauer data of spinel and garnet to a depth of 210 km from mantle xenoliths of the northern (N) and southeastern (SE) Slave craton (northern Canada). The profile transects three depth facies of peridotites that form segments of different bulk composition, represented by spinel peridotite, spinel–garnet peridotite, low-temperature garnet peridotite, high-temperature garnet peridotite, and pyroxenite. The shallow, more depleted N Slave spinel peridotite records lower oxygen fugacities compared to the deeper, less depleted N Slave spinel–garnet peridotite, consistent with their different spinel Fe³⁺ concentrations. Garnet peridotites show a general reduction in log fO₂ (FMQ)s with depth, where values for garnet peridotites are lower than those for spinel–garnet peridotites. There is a strong correlation between depletion and oxygen fugacity in the spinel peridotite facies, but little correlation in the garnet peridotite facies. The strong decrease in log fO₂ (FMQ) with depth that arises from the smaller partial molar volume of Fe³⁺ in garnet, and the observation of distinct slopes of log fO₂ (FMQ) with depth for spinel peridotite compared to spinel–garnet peridotite strongly suggest that oxygen fugacity in the cratonic peridotitic mantle is intrinsically controlled by iron equilibria involving garnet and spinel.

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Effect of oxygen fugacity on the etching rate of diamond crystals in silicate melt

Experimental data on the etching of diamond crystals in basaltic melt at 1130°C with variable oxygen fugacity in the environment are considered. The oxygen fugacity was set with the HM and NNO buffers. The study was carried out on a 0.6–0.8 mm fraction (powder) of natural diamond crystals. It has been established that, at the same temperature, the rate of diamond etching (oxidation) in silicate melt depends on the oxygen fugacity in the environment. The etching rate decreases with decline in the oxygen fugacity from the case where the melt comes into contact with atmospheric air to the conditions controlled by the HM and NNO buffers. Under the conditions of the HM and NNO buffers, oxidation was accompanied by surface graphitization of diamond crystals.