Cation order in olivines: Evidence from vibrational spectra

A simple theory is developed which relates cation ordering in the olivine structure to compositional trends in the vibrational spectra of olivines. Quantitative results for (Mg, Mn) and (Fe, Mn) olivines indicate that Mn²⁺ favors the M2 site relative to both Mg²⁺ and Fe²⁺.     

Calculation of muscovite-paragonite-alkali feldspar phase relations

Experimental data on K-Na exchange between NaCl-KCl-H₂O fluids and alkali feldspars or white micas, and end-member dehydration reactions of white mica (± quartz to alkali feldspar plus corundum (or Al₂SiO₅) and H₂O have been used to evaluate K-Na exchange potentials between coexisting white mica and alkali feldspar. Calculations using these exchange potentials and Margules parameters for excess molar Gibbs energies of alkali feld-spars and white micas have permitted the construction of a projected binary phase diagram for the white mica dehydration. Extrapolation to higher temperatures and pressures gives a topology wholly consistent with field evidence. The subsolidus univariant curves intersect H₂O-saturated minimum-melting curves. At pressures greater than about 6 kbar the common assemblage Ms+Or+Ab+Q could undergo H₂O-saturated minimum-melting at lower temperatures than the disappearance of paragonite or the kyanite-sillimanite isograd in more aluminous rocks. The apparent restriction of anatexis to rocks above the second sillimanite isograd may imply that activity of H₂O is usually less than unity in high-grade regional metamorphism.     

水 气二相渗流耦合模型全隐式联立求解

系统论述了水、气二相渗流耦合模型全隐式联立求解的方法与原理。该方法是将水相运动方程和气相运动方程左端的达西系数项、井点的气、水产量项作隐式处理，并将气相和水相方程联立起来进行求解，同时隐式求出压力和饱和度值。因此，收敛速度快，且无条件稳定。该方法应用于沁水盆地3^#煤层气井气，水产量的预测，效果良好。     

Effect of anorthite on granite phase relations: Experimental data and models

New experimental data on the effect of anorthite (An) on liquidus phase equilibria in the system Qz–Ab–Or are presented. The data were obtained for 5 wt% An added to variable Qz/Ab/Or compositions at 300 MPa and under H₂O-saturated conditions. Crystal–liquid equilibria were determined for 13 synthetic glass compositions made from gels in experiments performed between 660 and 750 °C in cold-seal pressure vessels. Forward and reversal experiments were systematically conducted on each composition to demonstrate equilibrium. A total of 51 charges was examined. Three crystalline phases, quartz, alkali feldspar and plagioclase appear on the H₂O-saturated liquidus surface. The determined minimum liquidus 5 wt% An “piercing” point (39% Qz, 33% Ab, 28% Or) is shifted away from the Ab apex toward the Qz–Or sideline when compared with the An-free 300 MPa H₂O-saturated minimum. This shift is of the same type as that observed at 100 MPa in the same system and at 200 MPa in a rhyolitic system. The new experimental results are used to test both empirical and thermodynamic models for silicic magmas. Empirical models reproduce reasonably well the new experimental data, although more sophisticated calculations schemes appear to be required to improve their accuracy. The new experimental results in the haplogranodiorite system are not well reproduced with the model of Holland and Powell (2001), mainly because plagioclase stability appears greatly enhanced in the model. Rhyolite-MELTS satisfactorily reproduces the Qz-, Pl- and Af-liquid phase equilibria, but model H₂O solubilities are significantly lower and crystallization temperatures higher than in experiments.     

Crossover of cation partitioning in olivines: a combination of ab initio and Monte Carlo study

We report studies based on a combination of ab initio electronic structure and Monte Carlo (MC) technique on the problem of cation partitioning among inequivalent octahedral sites, M1 and M2 in mixed olivines containing Mg²⁺ and Fe²⁺ ions. Our MC scheme uses interactions derived out of ab initio, density functional calculations carried out on measured crystal structure data. Our results show that there is no reversal of the preference of Fe for M1 over M2 as a function of temperature. Our findings do not agree with the experimental findings of Redfern et al. (Phys Chem Miner 27:630–637, 2000), but are in agreement with those of Heinemann et al. (Eur J Mineral 18:673–689, 2006) and Morozov et al. (Eur J Mineral 17:495–500, 2005).     

Alkali in phlogopite and amphibole and their effects on phase relations in metasomatized peridotites: a high-pressure study

Subsolidus phase relations for a K-doped lherzolite are investigated in the model system K₂O–Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O at 1.5–6.0 GPa and 680–1,000°C. Phlogopite is ubiquitous and coexists with Ca-amphibole up to 3.2 GPa and 900°C. High-pressure phlogopites show a peculiar mineral chemistry dependent on pressure: e.g., at 5.5 GPa and 680°C, excess of Si (up to 3.4 apfu) coupled with deficiency in Al (as low as 0.58 apfu) and K + Na (as low as 0.97 apfu), suggest a significant amount of a talc/10 Å phase component ([v]^XIISi₁K_?1Al _?1 ^IV , where [v]^XII is interlayer vacancy). Mixed layering or solid solution relations between high-pressure phlogopites and the 10 Å phase, Mg₃Si₄O₁₀(OH)₂ nH₂O, are envisaged. Phlogopite modal abundance, derived by weighted least squares, is maximum at high-pressure and relative low-temperature conditions and therefore along the slab–mantle interface (10.3 ± 0.7 wt.%, at 4.8 GPa, 680°C). In phlogopite-bearing systems, Ca-amphibole breaks down between 2.5 and 3.0 GPa, and 1,000°C, through the water conservative reaction 5(pa + 0.2 KNa_?1) + 17en + 15phl = (10di + 4jd) + 5py + 12fo + 20(phl + 0.2 talc), governed by bulk composition and pressure-dependent variations of K/OH in K-bearing phases and as a result, it does not necessarily imply a release of fluid.     

Calculation of subsolidus phase relations in carbonates and pyroxenes

This formulation of the free energy of mixing in a binary system takes as parameters a Bragg-Williams type cooperative disordering energy and the difference in free energy between different structures for the end-members. Subsolidus phase relations in carbonate systems such as CaCO₃—MgCO₃ and CdCO₃—MgCO₃ are calculated. Similar equations also reproduce the topologies of subsolidus phase relations in pyroxenes, including orthopyroxene-clinopyroxene phase boundaries in the enstatitediopside and ferrosilite-hedenbergite systems, the pigeonite-augite solvus, and the stability field of iron-free pigeonite.     

The case for a cognate,polybaric origin for kimberlitic olivines

Kimberlitic olivines typically show a continuous range in size and texture rather than two discrete populations. The cores of small euhedral olivines commonly provide the template for the final crystal shape, which in turn closely matches morphologies produced by crystallization from a moderately under-cooled magma. Cores and edges of the majority of all olivines define a continuous compositional field, which can be interpreted in terms of Raleigh crystallization. Marked chemical gradients at the olivine margins are linked to rapid physico-chemical changes to the magma associated with loss of volatiles during the late stages of emplacement. Thus, rapid crystallization of groundmass olivines would deplete the magma in Ni, but increase Ca activity. The latter would be enhanced by decreasing pressure coupled with loss of CO₂ from the carbonate-bearing kimberlite magma.For mantle olivines and the most refractory olivines in kimberlites (~ Fo₉₄) to be in equilibrium with bulk rock compositions matching those of Mg-rich macrocrystic and aphanitic kimberlites (Mg# ~ 88) requires a mineral-melt Mg–Fe distribution coefficient of 0.47. This is well within the experimentally determined range for this distribution coefficient in carbonate-bearing systems. In southern African post-Gondwana alkaline pipe clusters, the average bulk rock Mg# and composition of the associated most Mg-rich olivine both decrease sympathetically from the interior to the continental margin, which is also consistent with a cognate origin for the olivines.A kimberlite magma following a plausible P-T trajectory relative to the CO₂/H₂O peridotite solidus would initially experience superheating, resulting in partial resorption of early-formed olivines that crystallized on the cool conduit walls. It would become supersaturated as it crossed the carbonated peridotite “ledge”, resulting in tabular and hopper growth forms typical of euhedral olivine cores. With further ascent, the magma would once again become superheated, resulting in partial resorption of these cores. Thus, apparently complex textures and internal zonation patterns of kimberlitic olivines are predicted by a plausible magma P-T trajectory.     

Oxidised phase relations of a primitive basalt from Grenada,Lesser Antilles

A series of liquidus determinations is reported for a primitive arc basalt (15.4 wt % MgO, 45.5 wt % SiO₂) from Grenada, Lesser Antilles, at anhydrous, H₂O-undersaturated and H₂O-saturated conditions in the pressure range 1 atm to 1.7 GPa. \(\hbox{Fe}^{3+}/\Upsigma\hbox{Fe}\) of high-pressure experimental glasses as measured by μXANES ranges from 0.44 to 0.86, corresponding to oxygen fugacities (fO₂) between 3.2 and 7.8 log units above the nickel–nickel oxide redox buffer (NNO). 1-atm experiments conducted from NNO ? 2.5 to + 3.8 show that increasing fO₂ mainly increases the forsterite content (Fo) of olivine and has little effect on phase relations. The crystallisation sequence at lower crustal pressures for all water contents is forsteritic olivine + Cr-rich spinel followed by clinopyroxene. The anhydrous liquidus is depressed by 100 and 120 °C in the presence of 2.9 and 3.8 wt % H₂O, respectively. H₂O-undersaturated experiments at NNO + 3.2 to + 4.5 produce olivine of equivalent composition to the most primitive olivine phenocrysts in Grenadan picrites (Fo_91.4). We conclude that direct mantle melts originating beneath Grenada could be as oxidised as ~NNO + 3, consistent with the uppermost estimates from olivine–spinel oxybarometry of high Mg basalts. μXANES analyses of olivine-bearing experimental glasses are used to develop a semi-empirical oxybarometer based on the value of \({{K}_{D}}_{\rm ol-melt}^{\rm Fe-Mg}\) when all Fe is assumed to be in the Fe²⁺ state (\({K}_{D}^{{\rm Fe}_T}\)). The oxybarometer is tested on an independent data set and is able to reproduce experimental fO₂ to ≤1.2 log units. Experiments also show that the geochemically and petrographically distinct M- and C-series lavas on the island can be produced from hydrous melting of a common picritic source. Low pressures expand the olivine stability field at the expense of clinopyroxene, enriching an evolving melt in CaO and forcing differentiation to take place along a C-series liquid line of descent. Higher pressure conditions allow early and abundant clinopyroxene crystallisation, rapidly depleting the melt in both CaO and MgO, and thus creating the M-series.     

Experimental study of phase relations in a lithium-bearing fluorine-rich haplogranite and nepheline syenite system

Phase relations were investigated in the model water-saturated system Si-Al-Na-Li-F-O at high fluorine contents, a temperature of 800°C, and a pressure of 1 kbar. The obtained aluminosilicate melts are widely variable from quartz- to nepheline-normative compositions with agpaitic indexes both higher and lower than one. Various fluoride, aluminofluoride, and oxide phases were observed in the equilibrium assemblage depending on the melt composition: quartz and cryolite associate with the silica richest aluminosilicate melts, topaz and corundum coexist with peraluminous melts, and villiaumite was observed in highly peralkaline melts. Extensive immiscibility between aluminosilicate and aluminofluoride melts was observed in the system. Aluminofluoride melt coexists with quartz- and nepheline-normative aluminosilicate melts with agpaitic indexes (K _a) of 0.7–1.4. The composition of aluminosilicate melt in equilibrium with aluminofluoride melt ranges from 33 to 70 wt % SiO₂, from 12 to 24 wt % Al₂O₃, and from 5 to 16 wt % alkalis. The aluminofluoride melt is variable in composition, its Al/Na ratio ranges from 20/80 to 40/60 depending on the composition of the equilibrium aluminosilicate melt. The experimental aluminosilicate melts equilibrated with cryolite, topaz, and aluminofluoride melt coincide in major component proportions with the bulk compositions of cryolite- and topaz-bearing granites and melt inclusions in minerals.     

Manganese pyroxenoids and carbonates: Critical phase relations in metamorphic assemblages from the Alps

The compositions of coexisting pyroxmangites, rhodonites, rhodochrosites and manganese calcites in regional metamorphosed manganese cale-silicate marbles from Val Scerscen and Alagna were analysed by microprobe and permit definition of critical tie lines at metamorphic grades appropriate to temperatures between 400 and 450 °C.Variations in composition of coexisting mineral pairs in one and the same locality are attributed to variations in and not to metamorphic temperatures. From the analysed assemblages isothermal plots (with SiO₂ as excess component) were constructed for the system CaO-MnO-SiO₂-CO₂.     

Manganiferous phyllosilicate assemblages: occurrences,compositions and phase relations in metamorphosed Mn deposits

Mn-rich members of the pyrosmalite-family [(Mn, Fe)₈Si₆O₁₅(OH, Cl)₁₀], friedelite and schallerite have been identified as rock-forming minerals together with caryopilite, in several metamorphosed carbonate Mn-deposits. The phase assemblages and mineral compositions are described for eight of these localities each of which represents a distinct geologic situation. Friedelite is always Cl-bearing and occurs both as a prograde phase in low-grade metamorphic rocks (Pyrenees, Haute-Maurienne) and as a secondary phase formed by retrogressive replacement of primary anhydrous phases in higher-grade rocks. Schallerite, an Asbearing relative of friedelite, occurs in the greenschist metamorphic deposit of the Ködnitztal (Austria) together with other As-minerals. In these deposits, caryopilite is typically formed during retrograde metamorphism by alteration of, generally anhydrous, Mn-silicates. Based upon these occurrences, a qualitative petrogenetic grid for the system MnO-SiO₂-CO₂-H₂O with the phases friedelite, caryopilite, pyroxmangite/rhodonite, tephroite, rhodochrosite, quartz, CO₂, and H₂O is proposed. The phase relations imply that Cl- (or As-) free friedelite is not stable in hydrous systems with respect to caryopilite. From the mineral assemblages containing hydrous Mn silicates, waterrich fluids are inferred during the retrograde metamorphic evolution of the investigated deposits. Chemical data for Mn-rich chlorites, which are basically members of the clinochlore-pennantite series which coexist with the pyrosmalite minerals, show the absence of intermediate Mn/Mg ratios. This supports the existence of a miscibility gap as previously hypothesized by other authors.     

Cation distributions in olivines and orthopyroxenes an interlaboratory study

The determination of the (Fe, Mg)-cation distribution in important rock forming minerals such as olivines and orthopyroxenes from single crystal X-ray diffraction data is well established. The findings obtained from good quality data are, however, subject to the structure model, refinement strategy, data weighting etc. Moreover, they do not necessarily agree with those of comparable Mössbauer studies. In order to assess the reliability of the X-ray results, i.e. precision and accuracy of the site occupancies and ensuing cation distribution coefficients K _D , an interlaboratory study was undertaken. Two olivine and two orthopyroxene data sets, one experimental and three synthetic, were dispatched to interested applicants for structure refinements according to their own choice. Approximately correct structure parameters were given, but no information about the chemical composition, i.e. the Fe-content, was communicated. The total of 25 refinements for each data set, carried out with different programs, valence models, and weighting schemes, yielded some considerable differences between the results, which are summarized and discussed in terms of precision and accuracy. The uncertainties of the refined site occupancies, following from the qualities of the fits, are only realistic, when they are dominated by the statistical errors in the data. Errors in the independently refined Fe-concentrations on the M1-and M2-sites are not fully transferred to the thermodynamically relevant cation distribution coefficient. Therefore, correlations between the site occupancies, clearly recognizable from the compilations of all respective results, can be combined with an independently obtained chemical constraint (microprobe analysis) in order to yield reliable K _D -values with realistic uncertainties. In summary, all results indicate the need for multiple refinement techniques, if reliable results on the absolute scale are desired.     

Petrology and phase relations of the kyanite-eclogites from eastern Turkey

Eclogites are found as lenses or layers in the Precambrian gneiss terrain of the Bitlis Massif in eastern Turkey. Kyanite-eclogites from the region of Gablor Hill in the Bitlis Massif exhibit relatively minor alteration, and consist of garnet, omphacite, kyanite, zoisite, calcic amphibole, phengite, rutile and quartz. In terms of geological setting and mineral compositions, Gablor eclogites are very similar to eclogites from high-grade gneiss terrains. Metamorphic conditions during the eclogite crystallisation are determined as 625±35° C and 16±3 kbars. The coexistence of white mixa, omphacite and kyanite constrains between 0.4 and 1. Primary calcic amphiboles from the Gablor eclogites exhibit conflicting textures, indicating stable coexistence with, as well as growth from omphacite and garnet. This is explained by a buffering reaction between amphibole, garnet, omphacite, zoisite and kyanite during the eclogite crystallisation, whereby is controlled and buffered by the mineral assemblage.     

相位激电和时域激电对激电效应响应关系研究

相位激电法和时间域激电法都是以岩(矿)石的激发极化效应为基础的,极化相位和视极化率都是对岩(矿)石激发极化效应强弱的反映。这里通过数值模拟和矿区实测数据的分析,表明两者对可极化体激电效应的响应存在关联,在一定条件下,可建立关系式进行相互转换。     

Testing a solution to the King liberation model

A solution to the King liberation model is proposed and tested against the results of King and liberation of sphalerite, galena and chalcopyrite from a complex sulphide ore. For the King data, good agreement is shown. For the complex sulphide data, the trend is correct, but calibration is required for a close fit. A potentially important use of the model solution is to predict liberation size of an ore at the exploration stage.     

Melting relationships of Ni-Mg olivines and some geochemical implications

A complete series of solid solutions exists in the range Ni₂SiO₄-Mg₂SiO₄. Temperatures of beginning of melting increase with increasing content of Mg₂SiO₄. Solid solutions in the range N₁₀₀–N₅₀M₅₀ melt incongruently with the separation of NiO. In this range, ternary relations obtain. In the range N₅₀M₅₀–M₁₀₀ the system is binary. The behaviour of nickel in magmas is discussed in terms of the experimental data obtained, and it is concluded that nickel enters common olivine at the expense of iron rather than magnesium.     

Extrinsic and intrinsic mode of hydrogen occurrence in natural olivines: FTIR and TEM investigation

Olivine crystals from two mantle nodules in kimberlites (pipe Udachnaya and pipe Obnazennaya, Yakutiya, Siberia) were investigated using EMP, TEM, AEM and FTIR techniques to determine the mode of hydrogen occurrence in olivine. Olivine contains three types of nanometer-sized inclusions: “large” inclusions of hexagonal-like shape up to several hundred nm in size (1), lamellar defects (2) and small inclusions of hexagon-like shape up to several 10?nm in size (3). Lamellar defects and small inclusions are considered to be a “hydrous” olivine. All three types of inclusions contain OH^? or water, but they are different with respect to their phase composition. In “large” inclusions (1) hydrous magnesium silicates, such as serpentine?+?talc (“kerolite”?) and 10-Å phase?+?talc were identified. Lamellar defects (2) and small inclusions (3) are depleted in Mg and Fe compared to the olivine matrix, while the silica content is the same as that of olivine. Modulations in the periodicity of the olivine structure are observed in SAED patterns and HREM images of (2) and (3). The superperiodicity can be referred to OH^?-bearing point defect ordering in the olivine structure. If this is the case, the material of both lamellar defects and small inclusions can be assumed to be a “hydrous olivine” Mg_{2– x} v _x SiO₄H_{2 x} with a cation-deficient olivine crystal structure. Thus, both an extrinsic mode of hydrogen occurrence in olivine, such as nanometer-sized inclusions of OH^?-bearing magnesium silicates, and an intrinsic mode of hydrogen incorporation into the olivine structure, such as “hydrous olivine” in itself, were found. The data obtained here show that the OH absorption bands observed in olivine spectra at 3704(3717) and 3683(3688) cm^?1 can be unambiguously identified with serpentine; the band at 3677(3676) cm^?1 can be associated with talc. The absorption bands observed at 3591 and 3660?cm^?1 in olivine match those of the 10-Å phase at 3594, 3662 and 3666?cm^?1.     

Spinifex and swirling olivines in a komatiite lava lake,Munro Township,Canada

Spinifex veins, and veins filled with swirling, tabular olivine grains, intrude the upper part of a 120 m thick lava lake in Munro Township, Ontario, Canada. These veins are 20–200 cm wide, tens of metres long and are oriented roughly parallel to the upper surface of the lava lake. The spinifex texture differs from that found in simple layered komatiite flows: rather than increasing downwards, the size of skeletal olivine grains is greatest in the centres of the veins, or varies irregularly. Upper contacts meander and veinlets penetrate overlying rock; lower contacts are transitional. The other type of vein contains 50–70% of ∼5 mm long hopper olivine grains whose orientation varies widely to produce a swirling, contorted fabric. Both types of vein are believed to have formed when lava from the centre of the lake flowed into fractures in the solidified crust.The lava lake has a dunitic lower portion and an olivine porphyry upper portion. The composition of chill samples, the compositions of olivine phenocrysts, and variations in major element abundances throughout the unit are used to show that the lava originally was komatiite with about 22% MgO. The lava lake is overlain by mafic scorias and breccias with moderate vesicularity and welding structures suggesting eruption in shallow water.