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1.
Wadsleyite (β-(Mg,Fe)2SiO4) is a major constituent of the Earth's transition zone and is known to accommodate OH. The portion of the transition zone between 400–550 km could be an important source or sink for hydroxyl in plumes and slabs intersecting this region. Micro-infrared spectroscopy has been carried out on the β-phase and coexisting metastable olivine synthesized in a multianvil apparatus at 14 GPa and 1550–1650 K under hydrous conditions. Single-crystal and polycrystal specimens of both phases were analyzed in the 1800–8500 cm?1 frequency region to determine the speciation, abundances, and partitioning behavior of the hydrous components in coexisting β-phase and olivine. β-phase spectra consistently show three distinct OH bands at 3329, 3580, and 3615 cm?1. OH concentrations range from 10000–65000 H/106 Si. A strong positive correlation of grain size and extent of transformation with OH concentration in the β-phase indicates that grain-growth and transformation rates are enhanced in a hydrous environment. Olivine spectra are variable, but consistently show a prominent broad-band absorbance representing molecular H2O, consistent with the infrared signature of the starting material. OH concentrations in olivine range from <300–1400 H/106 Si. The highest OH concentrations measured for olivine and the β-phase may represent solubility limits, in which case the OH solubility ratio between these two phases is approximately 1∶40. Where both phases coexist and are undersaturated with OH, the partitioning ratio of OH between them is about 1∶100. The large solubility contrast between olivine and the β-phase suggests a mechanism for hydrating the transition zone via olivine carried down in subducting slabs. Plumes impinging on an OH-rich upper transition region could cause H2 or H2O to be released upon transformation of the β-phase to olivine, resulting in initiation of secondary upwellings. If dissolution of OH weakens the β-phase, and if OH is present in the mantle, the region between 400–550 km could be a zone of low viscosity.  相似文献   

2.
 An olivine grain from a peridotite nodule 9206 (Udachnaya kimberlite, Siberia) was investigated by TEM methods including AEM, HRTEM, SAED and EELS techniques. A previous study of the 9206 olivine sample revealed OH absorption bands in the IR spectrum and abundant nanometer-sized OH-bearing inclusions, of hexagonal-like or lamellar shape. Inclusions, which are several hundred nm in size, consist of 10 ? phase, talc and serpentine (chrysotile and lizardite). The lamellar (LI) and hexagon-like small inclusions of several ten nm in size (SI) are the topic of the present paper. AEM investigations of the inclusions reveal Mg, Fe and Si as cations only. The Mg/Si and Fe/Si atomic ratios are lower in the inclusions than in the host olivine. The Si concentration in the olivine host and both lamellar inclusions and small inclusions is the same. A pre-peak at 528eV was observed in EEL spectra of LI and SI, which is attributed to OH− or Fe3+. From these data it is concluded that there is a OH−- or Fe3+-bearing cation-deficient olivine-like phase present. HRTEM lattice fringe images of LI and SI exhibit modulated band-like contrasts, which are superimposed onto the olivine lattice. Diffraction patterns (Fourier-transforms) of the HREM images as well as SAED patterns show that the band-like contrasts in HRTEM images of the inclusions are caused by periodic modulations of the olivine lattice. Three kinds of superperiodicity in the olivine structure such as 2a, 3a and 3c, were observed in SAED patterns. The corresponding olivine supercells labelled here as Hy-2a, Hy-3a and Hy-3c were derived. The M1-vacancies located in the (100) and (001) octahedral layers of the olivine lattice are suggested to form ordered arrays of planar defects (PD), which cause the band-like contrasts in HRTEM patterns as well as the superperiodicity in the SAED patterns. The vacancy concentrations as well as the chemical composition of Hy-2a, Hy-3a and Hy-3c olivine supercells were calculated using crystal chemical approaches, assuming either {(OH)< O−V" Me−(OH)< O}↔, or {F e < Fe −H Me ′}↔ or {2F e < Fe −V Me "}↔ point defect associates. The calculated theoretical compositions Mg1.615Fe+2 0.135v0.25SiO4H0.5 (Hy-2a) and Mg1.54Fe2+ 0.12v0.33SiO4H0.66 (Hy-3a and Hy-3c) are in a good agreement with the AEM data on inclusions. Hy-2a, Hy-3a and Hy-3c are considered to be a hydrous olivine with the extended chemical formula (Mg1-yFe2+ y)2−xvxSiO4H2x. The crystal structure of hydrous olivine is proposed to be a modular olivine structure with Mg-vacant modules. The crystal chemical formula of hydrous olivines in terms of a modular structure can be written as [MgSiO4H2] · 3[Mg1.82Fe0.18SiO4] for Hy-2a, [MgSiO4H2] · 2[Mg1.82Fe0.18SiO4] for Hy-3a and Hy-3c. Hydrous olivine is suggested to be exsolved from the olivine 9206, which has been initially saturated by OH-bearing point defects. The olivine 9206 hydration as well as the following exsolution of hydrous olivine inclusions is suggested to occur at high pressure-high temperature conditions of the upper mantle. Received: 15 January 2001 / Accepted: 2 July 2001  相似文献   

3.
Hydrous species and the amount of water (OH? ions and crystal hydrate H2O) in structures of nominally anhydrous rock-forming minerals (olivine, ortho- and clinopyroxenes) were studied with Fourier spectroscopy in peridotite nodules (19 samples) from Cenozoic alkali basalts of the Baikal-Mongolia region (Dariganga Plateau, Taryat Depression, and Vitim Plateau). Single-crystal samples oriented relative to the crystallographic axes of minerals were examined with an FTIR spectrometer equipped with an IR microscope at the points of platelets free from fluid inclusions. FTIR spectra were measured in regions of stretching vibrations of OH? and H2O (3800–3000 cm?1) and deformation vibrations of H2O (1850–1450 cm?1). The water content in mineral structures was determined from integral intensities. To estimate the conditions of entrapment and loss of structural water in minerals, their chemical composition, including Fe2+ and Fe3+ contents, was determined with an electron microprobe analysis and Mössbauer spectroscopy. The bulk chemical composition of some nodules was determined with XRF and ICP MS. The total water content (OH? + H2O) varies from 150 to 1140 ppm in olivines, from 45 to 870 ppm in clinopyroxenes, and from 40 to 1100 ppm in orthopyroxenes. Both water species in the mineral structures are retained down to a depth of 150–160 km in wide temperature and pressure ranges (1100–1500 °C, 32–47 kbar) at the oxygen fugacity of ?1.4 to ?0.1 log units relative to that of the quartz-fayalite-magnetite buffer.  相似文献   

4.
Deformation experiments on olivine aggregates were performed under hydrous conditions using a deformation-DIA apparatus combined with synchrotron in situ X-ray observations at pressures of 1.5–9.8 GPa, temperatures of 1223–1800 K, and strain rates ranging from 0.8 × 10?5 to 7.5 × 10?5 s?1. The pressure and strain rate dependencies of the plasticity of hydrous olivine may be described by an activation volume of 17 ± 6 cm3 mol?1 and a stress exponent of 3.2 ± 0.6 at temperatures of 1323–1423 K. A comparison between previous data sets and our results at a normalized temperature and a strain rate showed that the creep strength of hydrous olivine deformed at 1323–1423 K is much weaker than that for the dislocation creep of water-saturated olivine and is similar to that for diffusional creep and dislocation-accommodated grain boundary sliding, while dislocation microstructures showing the [001] slip or the [001](100) slip system were developed. At temperatures of 1633–1800 K, a much stronger pressure effect on creep strength was observed for olivine with an activation volume of 27 ± 7 cm3 mol?1 assuming a stress exponent of 3.5, water fugacity exponent of 1.2, and activation energy of 520 kJ mol?1 (i.e., power-law dislocation creep of hydrous olivine). Because of the weak pressure dependence of the rheology of hydrous olivine at lower temperatures, water weakening of olivine could be effective in the deeper and colder part of Earth’s upper mantle.  相似文献   

5.
A suite of 11 gem-quality, optically completely clear garnet crystals with a broad variety of compositions in the space of the end members pyrope–almandine–spessartine–grossular–andradite–goldmanite were analyzed for trace amounts of “water” by nuclear reaction analysis, NRA, based on the reaction 1H(15N, αγ)12C, and by single-crystal absorption spectroscopy in the νOH vibrational range using microscope-FTIR-spectroscopic methods. The aim was to establish a calibration of the highly sensitive IR method with high areal resolution for “water” determination in garnets, by studying garnets of a wide compositional range, and to check for compositional dependencies of the integral molar absorptivities of the “water” component, ?int[1molH2O?1cm?2], in the nominally “water”-free garnets. The results of NRA show a broad variation of water contents in the range (14 ± 3) to (950 ± 80) wt ppmH2O, the values being low and very high for the garnet solid solutions (PyrAlm)SS and close-to-end-member GrossSS, respectively. There were no indications of inhomogeneities in the OH distribution, except possibly for one of the garnets (grossular, variety hessonite, from Tanzania). The quantitative evaluation of the complex νOH spectra, which showed similar shape only for members of the (PyrAlm)SS, yielded integral absorption coefficients, αint (cm?2), which allowed the calculation of integral molar absorptivities, ?int, using the “water” values of NRA. The ?int values obtained varied in a wide range but with no obvious correlation with the composition of the garnet except for the extremely high values, in the 104 range, of the two specimen with compositions close to end-member grossular. In all other garnets, ?int was in the 103 range with an average of ?int=3630±1580[1molH2O?1cm?2]. Therefore, this value is proposed for the use in routine “water” determinations of compositionally different garnets by the micro-IR method, except for garnets near to end-member grossular.  相似文献   

6.
We present new partition coefficients for various trace elements including Cl between olivine, pyroxenes, amphibole and coexisting chlorine-bearing aqueous fluid in a series of high-pressure experiments at 2 GPa between 900 and 1,300 °C in natural and synthetic systems. Diamond aggregates were added to the experimental capsule set-up in order to separate the fluid from the solid residue and enable in situ analysis of the quenched solute by LA–ICP–MS. The chlorine and fluorine contents in mantle minerals were measured by electron microprobe, and the nature of OH defects was investigated by infrared spectroscopy. Furthermore, a fluorine-rich olivine from one selected sample was investigated by TEM. Results reveal average Cl concentrations in olivine and pyroxenes around 20 ppm and up to 900 ppm F in olivine, making olivine an important repository of halogens in the mantle. Chlorine is always incompatible with Cl partition coefficients D Cl olivine/fluid varying between 10?5 and 10?3, whereas D Cl orthopyroxene/fluid and D Cl clinopyroxene/fluid are ~10?4 and D Cl amphibole/fluid is ~5 × 10?3. Furthermore, partitioning results for incompatible trace element show that compatibilities of trace elements are generally ordered as D amph/fluid ≈ D cpx/fluid > D opx/fluid > D ol/fluid but that D mineral/fluid for Li and P is very similar for all observed silicate phases. Infrared spectra of olivine synthesized in a F-free Ti-bearing system show absorption bands at 3,525 and ~3,570 cm?1. In F ± TiO2-bearing systems, additional absorption bands appear at ~3,535, ~3,595, 3,640 and 3,670 cm?1. Absorption bands at ~3,530 and ~3,570 cm?1, previously assigned to humite-like point defects, profit from low synthesis temperatures and the presence of F. The presence of planar defects could not be proved by TEM investigations, but dislocations in the olivine lattice were observed and are suggested to be an important site for halogen incorporation in olivine.  相似文献   

7.
The formation of extended planar defects in minerals such as olivine is related to high point defect concentration and can be driven by large gradients in chemical potential, where the energy of the system is lowered by the ordering of defects along specific planes in the crystal. The presence of extended defects has the potential to create the (apparently) anomalous ionic diffusion in olivine as reported recently (Spandler and O’Neill in Contrib Mineral Petrol 159(6):791–818, 2010). High-resolution transmission electron microscopy and energy-filtered imaging were done using experimental samples designed to examine the impact of a TiO2 and f O2 on the potential to form such defects in ferromagnesian olivine. Doped basalt (5 wt% TiO2)–olivine reaction couple experiments were run at 1 atm and 1,310 and 1,410 °C for 50 h at various f O2, ranging from 102 below to 102 above the quartz–fayalite–magnetite buffer. Our results show that extended planar defects in olivine, parallel to {101}ol and occurring in ordered “clusters” with a prolate spheroid geometry ~5–25 nm across and extending up to 150 nm into the olivine, are present near the olivine–glass interfaces in all of our experimental high-TiO2 basalt–olivine samples. Increased Ti content in the olivine is associated with the defects; ordering of Ti4+ and octahedral site vacancies leads to a two- or three-layer superstructure in the olivine. Defect nucleation and growth is driven by the large TiO2 chemical potential gradient across the phase boundary at the start of the experiments, which provides access to microstructures not otherwise present.  相似文献   

8.
The infrared (IR) spectra of gem-quality olivine crystals from Pakistan, formed in serpentinised dunitic rocks, are characterised by strongly pleochroic absorption bands at 3,613, 3,597, 3,580 and 3,566 cm?1. These bands are assigned to O-H stretching vibrations of OH point defects corresponding to H2O concentrations of about 35 wt ppm. Unlike other olivine spectra, the dominating bands are strongly polarised parallel to the b-axis. The unusual spectra type, excludes the presence of planar defects. This finding is supported by transmission electron microscopy. The 3,613 cm?1 band is related to vacant Si sites, the slightly lower energetic bands preferentially to vacant M2 sites. The exclusive presence of these bands is not only a characteristic feature of olivines treated under high P,T conditions equivalent to mantle environment, the presence of these bands in untreated natural olivine also indicates formation conditions equivalent to crustal rocks.  相似文献   

9.
Within a CM-like clast in the Plainview (H5) chondrite are two inclusions which have the distinctive morphologies of an Allende-like, coarse-grained CAI and an amoeboid olivine inclusion respectively. The compositions of the mineral components within the inclusions were ascertained in this microprobe study. The major constituents of the altered inclusions are calcite, Mg-Fe-rich phyllosilicates, Fe-Ti oxides, and an unusually Al-rich (21–32 wt% A12O3) phyllosilicate. Assuming the starting compositions for these inclusions suggested by their morphologies, namely, Ca-Al refractory-rich oxides and silicates, the alteration process would have required transport of Na, Cl, H2O, “CO2” and “FeO”. Because significant quantities of iron are required to produce the mineral assemblages now present from the inferred starting materials, and because of the presence of hydrous phases, it seems that liquid water was probably the medium in which the alteration reactions took place. The two possible sources of liquid water in meteorite parent bodies are primordially formed clay minerals and water ice. As yet neither source can be ruled out.  相似文献   

10.
The Tari-Misaka ultramafic complex, which is emplaced into the Paleozoic sediments and thermally metamorphosed by two younger granitic masses, is divided into four zones on the basis of the mineral assemblage. They are, in order of increasing metamorphic grade: Zone I antigorite-olivine-orthopyroxene-clinopyroxene. Zone II olivine-talc. Zone III olivine-anthophyllite. Zone IV olivine-orthopyroxene. Strongly serpentinized clinopyroxene-bearing harzburgite in Zone I is similar to ordinary Alpine-type harzburgite. In Zonne II, two kinds of olivine are recognized. One is Mg-rich olivine (Fo93 to Fo97) with opaque inclusions and is probably a recrystallization product of serpentine with talc. The other is Fe-rich olivine (Fo88 to Fo93) free of opaque inclusions and is probably a relic of the primary peridotite. Olivine in Zone III and Zone IV is also relatively Mg-rich (Fo91 to Fo95). Chromitite in Zone IV commonly has an assemblage, olivine+cordierite+Mg-Al spinel (Mg/Mg+Fe2+, more than 0.9). Enstatite is rare and coexists with less magnesian Mg-Al spinel (Mg/Mg+Fe2+, less than 0.9). Petrological and mineralogical characters of the ultramafic rocks can be well explained by thermal metamorphism of strongly serpentinized peridotite by granitic intrusion. Metamorphic zones are consistent with the experimental results in the system MgO-SiO2-H2O. The assemblage olivine+cordierite indicates that the metamorphism occurred at relatively low pressures (<3kb).  相似文献   

11.
The two textural varieties of olivine-rich Allende inclusions (rimmed and unrimmed olivine aggregates) consist primarily of a porous, fine-grained mafic constituent (inclusion matrix) that differs from the opaque meteorite matrix of CV3 chondrites by being relatively depleted in sulfides, metal grains, and (perhaps) carbonaceous material. Olivine is the most abundant mineral in Allende inclusion matrix; clinopyroxene, nepheline, sodalite, and Ti-Al-pyroxene occur in lesser amounts. Olivine in unrimmed olivine aggregates (Type 1A inclusions) is ferrous and has a narrow compositional range (Fo50–65). Olivine in rimmed olivine aggregates (Type 1B inclusions) is, on average, more magnesian, with a wider compositional range (Fo53–96). Olivine grains in the granular rims of Type 1B inclusions are zoned, with magnesian cores (Fo>80) and ferrous rinds (Fo<70). Ferrous olivines (Fo<65) in both varieties of inclusions commonly contain significant amounts of Al2O3 (as much as ~0.7 wt%), CaO (as much as ~0.4 wt%), and TiO2 (as much as ~0.2 wt%), refractory elements that probably occur in submicroscopic inclusions of Ca,Al,Ti-rich glass (rather than in the olivine crystal structure). Defocussed beam analyses of Allende matrix materials demonstrate that: (1) inclusion matrix in Type 1A inclusions is more enriched in olivine and FeO than inclusion matrix in the cores of Type 1B inclusions; (2) opaque matrix materials are depleted in feldspathoids and enriched in sulfides and metal grains relative to inclusion matrix; (3) the bulk compositions of Type 1A and Type 1B inclusions overlap; and (4) excluding sulfides and metal, the bulk compositions of Allende matrix materials cluster in a complementary pattern around the bulk composition of C1 chondrites.Inclusion matrix and meteorite matrix in Allende and other CV3 chondrites are probably relatively primitive nebular material, but a careful evaluation of the equilibrium condensation model suggests that these matrix materials do not consist of crystalline phases that formed under equilibrium conditions in a relatively cool gas of solar composition. Allende inclusion matrix is interpreted as an aggregate of condensates that formed under relatively oxidizing, non-equilibrium conditions from supercooled, supersaturated vapors produced during the vaporization of interstellar dust by aerodynamic drag heating in the solar nebula; CV3 meteorite matrix contains, in addition, a proportion of interstellar material that was heated (but not vaporized) in the nebula. Granular olivine in rimmed olivine aggregates may have formed during the recrystallization and incipient melting of aggregates of inclusion matrix in the nebula. The mineral chemistry of matrix olivine in Allende seems to have been established by three different processes: non-equilibrium vapor → solid condensation; recrystallization and partial melting in the nebula; and FeMg equilibration (without textural homogenization) in the meteorite parent body.  相似文献   

12.
From a total of 335 olivine crystal grains, crystallographically orientated platelets and, where possible, parallelepipeds were prepared, chemically analysed by electron microprobe, examined under the polarisation microscope, and studied by polarised FTIR microscope-absorption-spectrometry in the OH vibrational range, 3,000–3,800 cm–1. The 335 crystal grains were extracted from 174 different specimens of Yakutian upper mantle material, including 97 xenoliths that represent all the rock types occurring in all the kimberlites of the Siberian shield. The other specimens were mega- and macrocrysts or inclusions in diamonds and garnets. Analysis of the polarised OH-spectra allowed distinction between hydroxyl in non-intrinsic separate inclusions, NSI, and in isolated local or condensed extended defects, intrinsic to the olivines, ILD or CED, respectively. As the two latter types cannot be distinguished by vibrational spectroscopy, and as they are presumably interconnected by intracrystalline condensation reactions of the type n [ILD][CED]n, we propose to symbolise them as [ILD/CED]. Of the total of 70 polarised OH-bands that were found in the whole set, 17 are caused by NSI, 53 by [ILD/CED]. Total mean integrated OH-band intensities, (̄int)total with ̄int=(||a+||b+||c)int/3, were determined from the spectra. They yielded the contents of structurally unallocated water, using the recent calibration of the IR-method (Bell et al. 2003). The range is 0<wt. ppm (H2O)total<419. Olivines included in diamonds were found to be free of hydroxyl (detection limit of the single crystal IR-spectrometry, ca. 1 wt. ppm water). The total water contents of the different types of olivines increase in the sequence groundmass crystals < megacrysts < macrocrysts. NSI are: (1) Serpentine plus talc with OH in the range 3,704–3,657 cm–1, either polarised along a of the olivine matrix (Pbnm setting) or unpolarised. Approximately 232 olivines out of the 335 contain such NSI. Serpentine and talc occur mostly together, in rare cases one of them alone and if so, mostly talc. (2) Mg-edenite or Mg-pargasite occur rarely and with OH at 3,709–3,711 cm–1. NIS types (1) and (2) are presumably formed by metasomatic alterations of the host olivines, the orientated ones probably in the mantle, the unorientated ones during later stages. (3) The spectra of 23 olivine crystals, displayed specifically a OH-band, polarised c>a>b, at 3,327–3,328 cm–1, an energy typical of OH in hydrous wadsleyite. We assume this phase to be present as NIS in the respective olivines, possibly as relic phase. (4) Weak bands between 3,175 and 3,260 cm–1 polarised along c, are tentatively assigned to molecular water NSI with relatively strong hydrogen bonds to the matrix. We did not find larger clusters of molecular water, i.e. liquid-like water with its characteristic broad band centred at ca. 3,400 cm–1. We did also not find any humite minerals as an NSI. Of the 53 OH-bands intrinsic to olivine, the 29 most abundant and strong ones were subject to further analysis in terms of OH–-bearing structural defects [ILD/CED]. Nearly all these bands are strongly polarised along a. Two bands at 3,672 and 3,535 cm–1 are assigned to boron-related defects, [ILD/CED]B. Five bands at 3,573, 3,563, 3,541, 3,524 and 3,512 cm–1 are intensity-correlated and are assigned to Si-depleted titan-clinohumite-like defects, [ILD/CED](thl). The other, so far unidentified OH of [ILD/CED] are suggested to originate from OH– in different types of (Mg, Fe)-depleted defects recently predicted and discovered by TEM. These are called [ILD/CED](KWK). Eight mostly strong bands of them occur at energies higher than 3,573 cm–1, [ILD/CED](KWK)-H, 13 strong to medium strong bands occur below 3,500 cm–1, [ILD/CED](KWK)-L. Such intrinsic defects may occur alone, [ILD/CED](thl) and [ILD/CED](KWK)-H, or in different combinations with each other, [ILD/CED](KWK)-H+[ILD/CED](thl), [ILD/CED](KWK)-H+[ILD/CED](KWK)-L and [ILD/CED](KWK)-H+[ILD/CED](thl)+[ILD/CED](KWK)-L. Though there are indications that the occurrences of such types and combinations of the intrinsic OH–-bearing defects in the olivines are related to the types and genetic peculiarities of their host rocks, straightforward and simple correlations do not exist. The reasons for this and also for the great number of varieties of intrinsic [ILD/CED] are discussed.Editorial responsibility: J. Hoefs
S. S. MatsyukEmail:
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13.
Melt inclusions in olivine and pyroxene phenocrysts in kersantite and camptonite at Chhaktalao in Madhya Pradesh, India are mainly of the evolved type forming daughter minerals of olivine, pyroxene, plagioclase, spinel, mica, titanomagnetite and sulphides. Heating studies exhibit a temperature range from 1215° to 1245°C for the melt inclusions in olivine in camptonite and 1220–1245°C for olivine in kersantite. The temperature for melt inclusions in pyroxene ranged from 1000° to 1150°C in camptonite and 850–1100°C for pyroxene in kersantite. The bubble inside these melt inclusions is mainly CO2. The Th°C of CO2 into liquid phase occurred between 26° and 31°C in olivine and 25–30°C in pyroxene from kersantite and camptonite. The maximum density estimated is 0.72 g/cm3 and the minimum is 0.45 g/cm3. The depth of entrapment of the melt inclusion is estimated between 10–15 km. The pressure of entrapment of melt inclusion in olvine is 4.6 kbar where as that in pyroxene is 3.7 kbar. The lamprophyres in the Chhaktalao area are considered to be derived from low depth and low pressure region, possibly within spinel lherzolite zone.  相似文献   

14.
To investigate the solubility and the sites of incorporation of hydrogen in olivine as a function of point defect concentration, two-stage high-temperature annealing experiments have been carried out. The first annealing stage (the dry preannealing stage) was conducted at a total pressure of 0.1 MPa, a temperature of 1300° C and various oxygen fugacities in the range 10?11–10?4 MPa for times > 12 h. In these heat treatments, the samples were buffered against either orthopyroxene or magnesiowustite, or they remained unbuffered. The second annealing stage (the hydrothermal annealing stage) was performed at 300 MPa and 900–1050 ° C under a hydrogen fugacity of ～ 158 MPa for 1–5 h. Infrared spectra from the annealed samples revealed two distinct groups of bands. Group I bands occurred at wavenumbers in the range 3450–3650 cm?1, while Group II bands occurred in the range 3200–3450 cm?1. The hydrogen solubility associated with Group I bands is proportional to f O 2 to the 1/6 power for samples preannealed in contact with orthopyroxene, to the 1/3 power for samples preannealed in contact with magnesiowustite, and to the 1/13 power for samples preannealed in the absence of a solid-state buffer. The hydrogen concentration for Group II bands varies with f o 2 to the 1/3 power for opxbuffered samples, to the 1/2 power for mw-buffered samples, and to the 1/3 power for unbuffered samples. The dependence of hydrogen solubility on oxygen fugacity and orthopyroxene activity suggests that hydrogen is incorporated into the olivine structure via association with point defects. The presence of two distinct groups of absorption bands indicates that hydrogen is associated with two distinct lattice defects. The following point defect model for the mechanism of incorporation of hydrogen in olivine is consistent with these results: Hydrogen ions responsible for the Group I bands are associated with doubly charged oxygen interstitials, while hydrogen ions responsible for the Group II bands are associated with singly charged oxygen interstitials. Furthermore, the infrared bands observed in naturally derived olivines are present in spectra from our hydrothermally annealed crystals. Thus, the mechanisms of incorporation of hydrogen in olivine under geological conditions are the same as those operative under laboratory conditions. The maximum solubility reached in these experiments was ～ 360H/106Si, which corresponds to ～ 0.002 wt% of H2O. This value is a lower bound for the solubility of hydrogen in olivine under upper mantle conditions.  相似文献   

15.
The 10?-phase, Mg3Si4O10(OH)2 · nH2O, where n = 0.65÷2, belongs to the group of dense hydrous magnesium silicates (DHMS), which were produced in experiments and are regarded as hypothetical mineral carriers for H2O in the mantle. However, DHMS were almost never observed in nature. The only exception is the finding of the 10?-phase as nanoinclusions in olivines from mantle nodules in kimberlites. The inclusions with sizes of a few ten nanometers have a pseudohexagonal habit and are characterized by the presence of voids free of solids. The 10?-phase fills the equatorial parts of the inclusions, and, in the majority of inclusions, it is replaced by the low-pressure serpentine + talc assemblage. Based on the analysis of electron microscope images, a model was proposed for the solid-state formation of inclusions, the precursory material of which was transformed to the 10?-phase with the liberation of a water fluid. According to this model, the formation of hydrous nanoinclusions and their subsequent autoserpentinization occurred without the influx of H2O from the external medium through the mobilization of intrinsic hydroxyl-bearing point defects trapped during olivine crystallization. The subsequent autoserpentinization of the inclusions occurred during decompression owing to interaction between the inclusion material and the host olivine matrix. The process was accompanied by the partial exhaustion of the fluid phase and the replacement 10?-phase + H2O = Serp + Tc. The criterion for the credibility of the model is the conservation of the volume of material during the reaction at P = const and T = const. Original Russian Text ? N.R. Khisina, R. Wirth, 2008, published in Geokhimiya, 2008, No. 4, pp. 355–363.  相似文献   

16.
A large body of recent work has linked the origin of Si-Al-rich alkaline glass inclusions to metasomatic processes in the upper mantle. This study examines one possible origin for these glass inclusions, i.e., the dissolution of orthopyroxene in Si-poor alkaline (basanitic) melt. Equilibrium dissolution experiments between 0.4 and 2 GPa show that secondary glass compositions are only slightly Si enriched and are alkali poor relative to natural glass inclusions. However, disequilibrium experiments designed to examine dissolution of orthopyroxene by a basanitic melt under anhydrous, hydrous and CO2-bearing conditions show complex reaction zones consisting of olivine, ± clinopyroxene and Si-rich alkaline glass similar in composition to that seen in mantle xenoliths. Dissolution rates are rapid and dependent on volatile content. Experiments using an anhydrous solvent show time dependent dissolution rates that are related to variable diffusion rates caused by the saturation of clinopyroxene in experiments longer than 10 minutes. The reaction zone glass shows a close compositional correspondence with natural Si-rich alkaline glass in mantle-derived xenoliths. The most Si-and alkali-rich melts are restricted to pressures of 1 GPa and below under anhydrous and CO2-bearing conditions. At 2 GPa glass in hydrous experiments is still Si-␣and alkali-rich whereas glass in the anhydrous and CO2-bearing experiments is only slightly enriched in SiO2 and alkalis compared with the original solvent. In the low pressure region, anhydrous and hydrous solvent melts yield glass of similar composition whereas the glass from CO2-bearing experiments is less SiO2 rich. The mechanism of dissolution of orthopyroxene is complex involving rapid incongruent breakdown of the orthopyroxene, combined with olivine saturation in the reaction zone forming up to 60% olivine. Inward diffusion of CaO causes clinopyroxene saturation and uphill diffusion of Na and K give the glasses their strongly alkaline characteristics. Addition of Na and K also causes minor SiO2 enrichment of the reaction glass by increasing the phase volume of olivine. Olivine and clinopyroxene are transiently stable phases within the reaction zone. Clinopyroxene is precipitated from the reaction zone melt near the orthopyroxene crystal and redissolved in the outer part of the reaction zone. Olivine defines the thickness of the reaction zone and is progressively dissolved in the solvent as the orthopyroxene continues to dissolve. Although there are compelling reasons for supporting the hypothesis that Si-rich alkaline melts are produced in the mantle by orthopyroxene – melt reaction in the mantle, there are several complications particularly regarding quenching in of disequilibrium reaction zone compositions and the mobility of highly polymerized melts in the upper mantle. It is considered likely that formation of veins and pools of Si-rich alkaline glass by orthopyroxene – melt reaction is a common process during the ascent of xenoliths. However, reaction in situ within the mantle will lead to equilibration and therefore secondary melts will be only moderately siliceous and alkali poor. Received: 24 August 1998 / Accepted: 2 December 1998  相似文献   

17.
The oxygen isotopic distribution in an amoeboid olivine aggregate (AOA), TTA1-02, from the Allende CV3 chondrite has been determined by secondary ion mass spectrometry. The irregular shaped TTA1- 02 (5×3mm) consists mostly of olivine grains of ca. 5μm in diameter. Olivine grains of Mg-rich (Fo95) and Fe-rich (Fo60) composition are in direct contact with each other, with a sharp compositional boundary. Oxygen isotopic compositions of Fe-rich olivine grains are 16O-poor (Δ17O ≅ −5‰), whereas Mg-rich olivine is 16O-rich (Δ17O ≅ −25‰). Several Al-rich inclusions (<ca. 500 μm in diameter) are enclosed by olivine grains in the AOA. Oxygen isotopic compositions of spinel and fassaite in Al-rich inclusions are 16O-rich (Δ17O ≅ −20‰), whereas those of anorthite, nepheline and phyllosilicate are 16O-poor (Δ17O ≅ −5‰). We propose the following sequence of events during the formation of AOAs in the Allende meteorite: 1) Formation of Al-rich inclusions with 16O-rich oxygen isotopic composition; 2) Accretion of Mg-rich olivine grains with 16O-rich oxygen isotopic composition around Al-rich inclusions; 3) Accretion into parent body; and 4) Aqueous alteration in the parent body, which led to crystallization of 16O-poor minerals, Fe-rich olivine, anorthite, nepheline, and phyllosilicate. This is reflecting reactions among primary 16O-rich AOA minerals and aqueous fluid having 16O-poor oxygen isotopic composition. Fe-rich olivine grains precipitated from aqueous fluids, which partially dissolved pre-existing Mg-rich olivine grains. Sintering and Mg-Fe diffusion occurred during thermal metamorphism. Anorthite, nepheline and phyllosilicate in Al-rich inclusions replaced primary anorthite or melilite during the aqueous alteration stage.  相似文献   

18.
Olivine offers huge, largely untapped, potential for improving our understanding of magmatic and metasomatic processes. In particular, a wealth of information is contained in rare earth element (REE) mass fractions, which are well studied in other minerals. However, REE data for olivine are scarce, reflecting the difficulty associated with determining mass fractions in the low ng g?1 range and with controlling the effects of LREE contamination. We report an analytical procedure for measuring REEs in olivine using laser ablation quadrupole‐ICP‐MS that achieved limits of determination (LOD) at sub‐ng g?1 levels and biases of ~ 5–10%. Empirical partition coefficients (D values) calculated using the new olivine compositions agree with experimental values, indicating that the measured REEs are structurally bound in the olivine crystal lattice, rather than residing in micro‐inclusions. We conducted an initial survey of REE contents of olivine from mantle, metamorphic, magmatic and meteorite samples. REE mass fractions vary from 0.1 to double‐digit ng g?1 levels. Heavy REEs vary from low mass fractions in meteoritic samples, through variably enriched peridotitic olivine to high mass fractions in magmatic olivines, with fayalitic olivines showing the highest levels. The variable enrichment in HREEs demonstrates that olivine REE patterns have petrological utility.  相似文献   

19.
 Recently, the Hy-2a hydrous olivine (MgH2 SiO4)·3(Mg2SiO4) occurring as nanometre-sized inclusions in mantle olivines has been found by TEM, and has been suggested to be a new DHMS phase (Khisina et al. 2001). A model of the crystal structure of Hy-2a has been proposed as a 2a-superstructure of olivine with one Me2+ -vacant octahedral layer in the (1 0 0) plane per Hy-2a unit cell (Khisina and Wirth 2002). In the present study the crystal structure of Hy-2a hydrous olivine is optimized by ab initio calculations. The aims of this study are: (1) verification of the suggested models of Hy-2a hydrous olivine structure; (2) calculation of the most stable configurations for Hy-2a structure with minimum static lattice energy, by assuming a possible formation of Me2+ vacancies in either M1 or M2 octahedral sites; (3) determination of the position of protons and hydrogen bonds in the Hy-2a structure. Several different possible configurations of the Hy-2a structure are optimized. The results support the idea of a stable olivine structure with ordered planar-segregated OH-bearing defects oriented parallel to (1 0 0). The data obtained indicate a preferred stability of the Hy-2a structure with the protons associated with M1 vacancies and bonded with O1 and O2 oxygen sites. The relative energy values of the optimized Hy-2a structure configurations correlate as a rule with the average shifts of atoms from their positions in pure forsterite structure. Received: 7 February 2002 / Accepted: 23 October 2002  相似文献   

20.
A suite of more than 200 garnet single crystals, extracted from 150 xenoliths, covering the whole range of types of garnet parageneses in mantle xenoliths so far known from kimberlites of the Siberian platform and collected from nearly all the kimberlite pipes known in that tectonic unit, as well as some garnets found as inclusions in diamonds and olivine megacrysts from such kimberlites, were studied by means of electron microprobe analysis and single-crystal IR absorption spectroscopy in the v OH vibrational range in search of the occurrence, energy and intensity of the v OH bands of hydroxyl defects in such garnets and its potential use in an elucidation of the nature of the fluid phase in the mantle beneath the Siberian platform. The v OH single-crystal spectra show either one or a combination of two or more of the following major v OH bands, I 3645–3662 cm−1, II 3561–3583 cm−1, III 3515–3527 cm−1, and minor bands, Ia 3623–3631 cm−1, IIa 3593–3607 cm−1. The type of combination of such bands in the spectrum of a specific garnet depends on the type of the rock series of the host xenolith, Mg, Mg-Ca, Ca, Mg-Fe, or alkremite, on the xenolith type as well as on the chemical composition of the respective garnet. Nearly all garnets contain band systems I and II. Band system III occurs in Ti-rich garnets, with wt% TiO2 > ca. 0.4, from xenoliths of the Mg-Ca and Mg-Fe series, only. The v OH spectra do not correspond to those of OH− defects in synthetic pyropes or natural ultra-high pressure garnets from diamondiferous metamorphics. There were no indications of v OH from inclusions of other minerals within the selected 60 × 60 μm measuring areas in the garnets. The v OH spectra of pyrope-knorringite- and pyrope-knorringite-uvarovite-rich garnets included in diamonds do not show band systems I to III. Instead, they exhibit one weak, broad band (Δv OH 200–460 cm−1) near 3570 cm−1, a result that was also obtained on pyrope-knorringite-rich garnets extracted from two olivine megacrysts. The quantitative evaluation, on the basis of relevant existing calibrational data (Bell et al. 1995), of the sum of integral intensities of all v OH bonds of the garnets studied yielded a wide range of “water” concentrations within the set of the different garnets, between values below the detection limit of our single-crystal IR method, near 2 × 10−4 wt%, up to 163 × 10−4 wt%. The “water” contents vary in a complex manner in garnets from different xenolith types, obviously depending on a large number of constraints, inherent in the crystal chemistry as well as the formation conditions of the garnets during the crystallization of their mantle host rocks. Secondary alteration effects during uplift of the kimberlite, play, if any, only a minor role. Despite the very complex pattern of the “water” contents of the garnets, preventing an evaluation of a straightforward correlation between “water” contents of the garnets and the composition of the mantle's fluid phase during garnet formation, at least two general conclusions could be drawn: (1) the wide variation of “water” contents in garnets is not indicative of regional or local differences in the composition of the mantle's fluid phase; (2) garnets formed in the high-pressure/high-temperature diamond-pyrope facies invariably contain significantly lower amounts of “water” than garnets formed under the conditions of the graphite-pyrope facies. This latter result (2) may point to significantly lower f H2O and f O2 in the former as compared to the latter facies. Received: 25 November 1997 / Accepted: 9 March 1998  相似文献   

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