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1.
A crystallographic and m?ssbauer spectroscopy study of Fe   总被引：1，自引：0，他引：1  
The crystal chemistry of garnet solid solutions on the Fe 3 2+ Al2Si3O12-Fe 3 2+ Fe 2 3+ Si3O12 (almandine-“skiagite”) and Ca3Fe 2 3+ Si3O12-Fe 3 2+ Fe 2 3+ Si3O12 (andradite-“skiagite”) joins have been investigated by single-crystal X-ray structure refinements and M?ssbauer spectroscopy. Together, these two solid solution series encompass the complete range in Fe3+/ΣFe from 0.0 to 1.0. All garnets are isotropic and were re0fined in the Ia d space group. Small excess volumes of mixing are observed in andradite-“skiagite” solid solutions (W v =1.0±0.2 cm3 mol-1) and along the almandine-“skiagite” join (W v =-0.77±0.17cm3 mol-1). The octahedral (Al, Fe3+)-O bond lengths show a much greater variation across the almandine-skiagite join compared to the andradite-skiagite garnets. The dodecahedral (X)-O bond lengths show the opposite behaviour. In andradite-“skiagite” solid solutions, the octahedral site passes from being flattened to elongated parallel to the 3 axis of symmetry with increasing “skiagite” content. A perfect octahedron occurs in a composition of ≈35 mol% “skiagite”. The occupancy of the neighboring dodecahedral sites has the greatest effect on octahedral distortion and vice versa. The M?ssbauer hyperfine parameters of Fe2+remain constant in both solid solutions. The hyperfine parameters of Fe3+ (at room temperature: centre shift=0.32–0.40 mm/sec, quadrupole splitting (QS)≈0.21–0.55 mm/ sec) indicate that all Fe3+ is in octahedral coordination. The Fe3+ parameters are nearly constant in almandine-“skiagite” solid solutions, but vary significantly across the andradite-“skiagite” join. The structural unit that contributes to the electric field gradient of the octahedral site is different from that of the coordinating oxygen polyhedron, probably involving the neighboring dodeca-hedral sites.  相似文献   

2.
Phase transformations in a natural sample of hedenbergite ((Ca0.93Fe0.61Mn0.34Mg0.08Na0.01Zn0.02Al0.003)Si2O6) have been studied by X-ray diffraction up to 40 GPa at ∼ 1200°C in a diamond anvil cell interfaced with a laser heating system. The starting hedenbergite phase decomposed into a garnet plus γ-spinel and stishovite at ∼ 14 GPa; then into garnet plus stishovite and wüstite at ∼ 18 GPa; and finally into perovskite plus stishovite and wüstite at pressures higher than ∼ 24 GPa. On decompression to 0.1 MPa, all the high pressure phases are retained except for the cubic perovskite, which reverts back into the ɛ-CaSiO3 phase, in accordance with previous reports. Energy-dispersive SEM analyses show that the garnet is present as a calcium-rich ABO 3-type phase. As no garnet phase has been previously observed either in pure CaSiO3 or in pure CaMgSi2O6, it appears that the observed calcium-rich garnet phase has been stabilized by the presence of other cations such as the Na+, Zn2+, Mn2+, Fe2+, Mn3+, Fe3+ and Al3+.  相似文献   

3.
Unusual Ti–Cr–Zr-rich garnet crystals from high-temperature melilitic skarn of the Maronia area, western Thrace, Greece, were investigated by electron-microprobe analysis, powder and single-crystal X-ray diffraction, IR, Raman and Mössbauer spectroscopy. Chemical data showed that the garnets contain up to 8 wt.% TiO2, 8 wt.% Cr2O3 and 4 wt.% ZrO2, representing a solid solution of andradite (Ca3Fe3+ 2Si3O12 ≈46 mol%), uvarovite (Ca3Cr2Si3O12 ≈23 mol%), grossular (Ca3Al2Si3O12 ≈10 mol%), schorlomite (Ca3Ti2[Si,(Fe3+,Al3+)2]O12 ≈15 mol%), and kimzeyite (Ca3Zr2[Si,Al2]3O12 ≈6 mol%). The Mössbauer analysis showed that the total Fe is ferric, preferentially located at the octahedral site and to a smaller extent at the tetrahedral site. Single-crystal XRD analysis, Raman and IR spectroscopy verified substitution of Si mainly by Al3+, Fe3+ and Ti4+. Cr3+ and Zr4+ are found at the octahedral site along with Fe3+, Al3+ and Ti4+. The measured H2O content is 0.20 wt.%. The analytical data suggest that the structural formula of the Maronia garnet can be given as: (Ca2.99Mg0.03)Σ=3.02(Fe3+ 0.67Cr0.54Al0.33Ti0.29Zr0.15)Σ=1.98(Si2.42Ti0.24Fe0.18Al0.14)Σ=2.98O12OH0.11. Ti-rich garnets are not common and their crystal chemistry is still under investigation. The present work presents new evidence that will enable the elucidation of the structural chemistry of Ti- and Cr-rich garnets.  相似文献   

4.
 In order to develop a model for simulating naturally occurring chromian spinel compositions, we have processed published experimental data on chromian spinel-melt equilibrium. Out of 259 co-existing spinel-melt experiments reported in the literature, we have selected 118 compositions on the basis of run time, melt composition and experimental technique. These data cover a range of temperatures 1150–1500° C, oxygen fugacities of −13<log f O2< −0.7, and bulk compositions ranging from basalt and norite, to komatiite. Six major spinel components with Cr3+, Al3+, Ti4+, Mg2+, Fe3+ and Fe2+-bearing end-members were considered for the purpose of describing chromite saturation as a function of melt composition, temperature and oxygen fugacity at 1 atmosphere pressure (0.101 MPa). The empirically calibrated mineral-melt expression based on multiple linear regressions is: K Sp i =A/T(K)+B log f O2+C ln (Fe3+/Fe2+)L+D ln R L +E, where K Sp i is an equilibrium constant and R L is a melt structure-chemical parameter (MSCP). Twenty-eight forms of equilibrium constants were considered, including single distribution coefficients, exchange equilibrium constants, formation constants for AB2O4 components, as well as simple “spinel cation ratios”. For each form of the equilibrium constants, a set of 16 combinations of the MSCPs have been investigated. The MSCP is present in the form of composite ratios [e.g., Si/O, NBO/T,(Al+Si)/Si, or (Na+K)/Al] or as simple cation ratios (e.g., Mg/Fe2+). For the calculation of Fe3+ and Fe2+ species in silicate melts, we used existing equations, whereas the Fe3+/Fe2+ ratio of spinels was calculated from the spinel stoichiometry. The regression parameters that best repoduce the experimental data were for the following constants: (Fe3+/Fe2+) Sp , (Mg/Fe2+) Sp /(Mg/Fe2+) L , (Cr/Al) Sp / (Cr/Al) L , K FeCr2O4, and Ti Sp /Ti L . These expressions have been combined into a single program called SPINMELT, which calculates chromite crystallization temperature and composition at a given f O2 with an average accuracy of ∼10° C and 1–2 mol%. An example of the use of SPINMELT is presented for a magma parental to the Bushveld Complex. Received: 30 May 1995/Accepted: 1 November 1995  相似文献   

5.
Summary The first natural tourmaline (because tourmaline with [4]B has also been synthesized, we distinguish here between natural and synthetic tourmaline) that has been unequivocally demonstrated to contain B as a substituent at the T sites was described from Koralpe, Styria, Austria. This colourless B-rich olenite occurs as rims overgrowing schorl (black crystals up to a few cm) that has not yet been structurally characterized. A crystal structure refinement (R = 0.019) of this Al-rich schorl shows that [4]B occurs in the overgrown schorl; the optimized occupants of the atomic positions yield X (Na0.64Ca0.10K0.06□0.20) Y (Fe2+ 1.72Al1.08Ti0.11Zn0.03□0.06) Z (Al5.70Mg0.20Fe0.08 2+Mn0.02) ([3]BO3)3.00 T (Si5.76 [4]B0.24)O18 [F0.11(OH)3.31O0.58]. This is the first known (Al-rich) schorl where a structure refinement has detected [4]B. Comparing the structure refinements and the chemical composition of the Koralpe schorl and other [4]B-bearing tourmalines with tourmalines which contain no [4]B, it is of interest that only structure refinements of tourmalines which are low in magnesium and with a higher component of olenite show substantial amounts of [4]B; the role of Mg in controlling the amount of [4]B is not known, but it seems that an Al-component on the Y site (olenite-component), a boron-enriched environment and special P-T-t conditions are necessary to get tourmaline with substantial amounts of [4]B. Received July 7, 2000; revised version accepted June 6, 2001  相似文献   

6.
An integrated geochemical analysis of the well-exposed Pine Creek, California tungsten skarn deposit has been undertaken to evaluate changes in chemical gradients across various lithologies. Thermodynamic calculations using available experimental and thermodynamic data allow limits to be assigned to the activities of important chemical components in the metasomatic environment. Quantifiable changes in “non-volatile” component activites (CaO, MgO, Al2O3, Fe2O3, WO3) and in fugacities (O2, F2) have been traced across the system. The activities of Al2O3, Fe2O3 and WO3 generally increase from the marble (<102, <10−6, <10−5 respectively), through the outer skarn zone and into the massive garnet skarn (10−1.7±0.3, 10−3.4±0.4, 10−4.8±0.1) While CaO and MgO activities decrease for the same traverse from 10−5 and 10−2.1±1 respectively, to <10−5.7 and <10−3. Calculated oxygen fugacities are 10−23.5+1.0 at T=800 K (527° C), about one log unit below QFM, and more reducing than that required by Mt-Py-Po. The high variance of the garnet-pyroxene-quartz assemblages adds sufficient uncertainty to the calculated activities for individual specimens that only the large-scale trends survive the small-scale scatter. None of the chemical variables emerge as major independent or controlling factors for the mineralogy or phase compositions. Changes in the activity of one component may be offset by compensatory changes in another resulting in an environment that, while different from Pine Creek, could still host scheelite mineralization. Mass balance calculations indicate that the exposed endoskarn cannot have supplied the necessary chemical components to convert the country rock to skarn.  相似文献   

7.
Examination of schorlomite from ijolite at Magnet Cove (USA) and silicocarbonatite at Afrikanda (Russia), using electron-microprobe and hydrogen analyses, X-ray diffraction and Mössbauer spectroscopy, shows the complexity of substitution mechanisms operating in Ti-rich garnets. These substitutions involve incorporation of Na in the eightfold-coordinated X site, Fe2+ and Mg in the octahedrally coordinated Y site, and Fe3+, Al and Fe2+ in the tetrahedrally coordinated Z site. Substitutions Ti4+Fe3+Fe3+–1Si–1 and Ti4+Al3+Fe3+–1Si–1 are of major significance to the crystal chemistry of schorlomite, whereas Fe2+ enters the Z site in relatively minor quantities (<3% Fe). There is no evidence (either structural or indirect, such as discrepancies between the measured and calculated Fe2+ contents) for the presence of [6]Ti3+ or [4]Ti4+ in schorlomite. The simplified general formula of schorlomite can be written as Ca3Ti4+2[Si3-x(Fe3+,Al,Fe2+)xO12], keeping in mind that the notion of end-member composition is inapplicable to this mineral. In the published analyses of schorlomite with low to moderate Zr contents, x ranges from 0.6 to 1.0, i.e. Ti4+ in the Y site is <2 and accompanied by appreciable amounts of lower-charged cations (in particular, Fe3+, Fe2+ and Mg). For classification purposes, the mole percentage of schorlomite can be determined as the amount of [6]Ti4+, balanced by substitutions in the Z site, relative to the total occupancy in the Y site: ([6]Ti4+–[6]Fe2+–[6]Mg2+– [8]Na+)/2. In addition to the predominant schorlomite component, the crystals examined in this work contain significant (>15 mol.%) proportions of andradite (Ca3Fe3+2Si3O12), morimotoite (Ca3Fe2+TiSi3O12), and Ca3MgTiSi3O12. The importance of accurate quantitative determination and assignment of Fe, Ti and other cations to the crystallographic sites for petrogenetic studies is discussed.
A. R. ChakhmouradianEmail: Phone: +1-204-4747278Fax: +1-204-4747623
  相似文献   

8.
This paper attempts to illustrate the chemical variations of metamorphic hornblendes regarding host rocks and prograde variations. Changes related to bulk chemistry (orthoamphibolites) mainly concern Si, Al, Mg, Fetot and Ca. The Mg, Fe2+ and Fe3+ contents of hornblendes are, however, not strictly related to host rook compositions and Mg enrichments are correlated with increasing Fe3+ contents in the amphiboles. Thus, variations of oxygen fugacity may control the Mg contents of the Ca amphiboles studied but this does not show clear relations with the prograde metamorphism. The most sensitive but irregular variation related to the metamorphic conditions is the prograde enrichment of the alkalis into the A vacant position and an increase of the (Na+K)tot/Na+K+Ca ratios of the amphiboles. Increasing Ti and AlIV contents as well as decreasing AlVI concentrations are also, but much less evidently, related to increasing T and P. A variation trend from tschermakitic to edenitic hornblendes may be drawn using Shido's end members calculation; this tendency and the relative deficiency of AlVI contents in the low-grade members suggests that the amphiboles studied were subjected to conditions of a low-pressure metamorphism type. Such a conclusion is in agreement with the occurrence of andalusite-cordierite/sillimanite-cordierite associations in the metapelitic rocks, and the absence of Fe-rich garnet and epidote from the orthoamphibolites of the amphibolite facies at Aracena. Comparisons with Ca amphiboles from other metamorphic areas show, in agreement with various authors, that Abukuma hornblendes are similar to those encountered in high-grade thermal aureoles and tonalitic intrusives but different from the hornblendes of Barrovian metamorphism types.  相似文献   

9.
In order to explore possible quantitative relations between crystal field stabilization energy, CFSE, and partitioning behaviour of the 3d 6-configured Fe2+ ion, a suite of 29 paragenetic rock-forming minerals from 12 high-grade metamorphic rock samples of the Ukrainian shield, including the parageneses garnet/orthopyroxene/clinopyroxene (2x), orthopyroxene/clinopyroxene, garnet/clinopyroxene, garnet/orthopyroxene/biotite, garnet/biotite, garnet/cordierite, garnet/cordierite/biotite, garnet/orthopyroxene/clinopyroxene/Ca-amphibole, Ca-amphibole/biotite (retrograde), was studied by electron microprobe analysis to obtain the respective K D Fe2+ (Ph1/Ph2) values and by polarized single crystal electronic absorption spectroscopy to evaluate the respective CFSEFe2+ values. Other than in the case of Cr3+, a clear quantitative relation between K D (Ph1/Ph2) and the ΔCFSE(Ph1/Ph2) was only observed when geometrical factors, mainly the volume of crystallographic sites and ionic radii of ions competing in the partitioning process, are similar in the respective two paragenetic phases to within 15–20%. In such cases, the ΔCFSEFe2+ contribution to K D (Ph1/Ph2) amounts to 0.1 to 0.2 log K D per 100 cm−1ΔCFSE. The conclusion is that ΔCFSEFe2+ plays only a secondary role after geometrical factors, in the partitioning behaviour of Fe2+. The reason for this is seen in the facts that, compared to the 3d  3-configured Cr3+ ion, CFSE of the 3d 6-configured Fe2+ amounts only to 20–25%, and that the former ion enters only octahedral sites with similar geometrical properties in the paragenetic mineral phases. Received: 17 November 1998 / Accepted: 28 June 1999  相似文献   

10.
Sogdianite, a double-ring silicate of composition ( \textZr0. 7 6 \textTi0. 3 84 + \textFe0. 7 33 + \textAl0.13 )\Upsigma = 2 ( \square 1. 1 5 \textNa0. 8 5 )\Upsigma = 2 \textK[\textLi 3 \textSi 1 2 \textO 30 ] ( {\text{Zr}}_{0. 7 6} {\text{Ti}}_{0. 3 8}^{4 + } {\text{Fe}}_{0. 7 3}^{3 + } {\text{Al}}_{0.13} )_{\Upsigma = 2} \left( {\square_{ 1. 1 5} {\text{Na}}_{0. 8 5} } \right)_{\Upsigma = 2} {\text{K}}[{\text{Li}}_{ 3} {\text{Si}}_{ 1 2} {\text{O}}_{ 30} ] from Dara-i-Pioz, Tadjikistan, was studied by the combined application of 57Fe M?ssbauer spectroscopy and electronic structure calculations. The M?ssbauer spectrum confirms published microprobe and X-ray single-crystal diffraction results that indicate that Fe3+ is located at the octahedral A-site and that no Fe2+ is present. Both the measured and calculated quadrupole splitting, ΔE Q, for Fe3+ are virtually 0 mm s−1. Such a value is unusually small for a silicate and it is the same as the ΔE Q value for Fe3+ in structurally related sugilite. This result is traced back to the nearly regular octahedral coordination geometry corresponding to a very symmetric electric field gradient around Fe3+. A crystal chemical interpretation for the regular octahedral geometry and the resulting low ΔE Q value for Fe3+ in the M?ssbauer spectrum of sogdianite is that structural strain is largely “taken up” by weak Li–O bonds permitting highly distorted LiO4 tetrahedra. Weak Li–O bonding allows the edge-shared more strongly bonded Fe3+O6 octahedra to remain regular in geometry. This may be a typical property for all double-ring silicates with tetrahedrally coordinated Li.  相似文献   

11.
New experimental amphibole/melt partition coefficients from a variety of geologically relevant amphibole (pargasite, kaersutite, and K-richterite) and melt compositions obtained under conditions of interest to upper-mantle studies are combined with the results of X-ray single-crystal structure refinement. The ideal cation radii (r0), calculated using the lattice-site elastic-strain model of Blundy and Wood (1994) under the hypothesis of complete REE (rare earth elements) ordering at [8]M4, mostly differ significantly from those obtained from both the structure refinement and the ionic radius of [8]Ca2+. Heavier REE may also strongly deviate from the parabolic trends defined by the other REE. On the basis of the crystal-chemical knowledge of major-element site-preference in amphibole and the occurrence of two sites with different co-ordination within the M4 cavity (M4 for Ca and Na, M4′ for Fe2+ and Mg), we propose a new model for REE incorporation. LREE order at the [8]M4 site, whereas HREE prefer the M4′ site with lower co-ordination in amphiboles with a significant cummingtonite component, and may also enter the M2 octahedron, at least in richterite. This more complex model is consistent with the observed Amph/LD, and drops the usual assumption that REE behave as a homogeneous group and order at the M4 site. The availability of multiple crystal-chemical mechanisms for REE3+ incorporation explains why measured and estimated Amph/LDHREE may differ by up to one order of magnitude. When REE enter two different sites within the same cavity, a fit performed on the basis of a single curve may appear correct, but the values obtained for r0 are biased towards those of the dominant site, and the Young's modulus is underestimated. When REE are incorporated in multiple sites in different cavities, the observed pattern cannot be reduced to a single curve, and the partition coefficients of heavy REE would be strongly underestimated by a single-site fit. The simplistic assumption that REE occupy a single site within the amphibole structure can thus substantially bias predictive models based on the elastic-strain theory. Our combined approach allows linkage between fine-scale site preference and the macroscopic properties of minerals and provides more reliable predictive models for mineral/melt partitioning. After the possible site-assignments have been identified, the shape of the Onuma curves constructed from accurately determined Amph/LDREE now allows the active mechanisms for REE incorporation in amphiboles to be recognised even where site populations are not available. The REE preference for polyhedra with smaller size and lower co-ordination than those occupied by Ca invalidates the general idea that Ca acts as a “carrier” for REE. Received: 17 March 1999 / Accepted: 11 June 1999  相似文献   

12.
 Three chlorite-rich and one garnet-pyroxenite xenolith from the diatreme at Moses Rock, Utah, document storage and transport of water and consequent metasomatism in the mantle within the stability field of garnet peridotite, probably at depths of at least 75 km. Three mineral assemblages are present in zones in one chlorite-rich xenolith: in that xenolith, an assemblage of chlorite+enstatite+diopside+ ilmenite+titanian chondrodite is separated by diop- side+“talc” from an assemblage of chlorite+diopside+ilmenite+pyrite. Euhedral grains of enstatite (0.02% Al2O3, 0.05% CaO)+diopside record low temperatures, and high Mn/Fe in these pyroxenes was caused by growth in chlorite-dominated rock. Derivation from garnet lherzolite is established by relict pyrope (Py71Gr11Alm18). The “talc” has Fe/Mg unusually high relative to that of associated chlorite, and electron probe analyses of the “talc” sum low, consistent with excess water; the unusual composition may be due solely to alteration and consequent submicroscopic intergrowths of other phases, but the “talc” could be an analogue of the high-pressure synthetic 10-Å phase. Garnet pyroxenite has a retrograde assemblage of chlorite-garnet-omphacite. The chlorite-rich rocks formed at contacts between garnet peridotite and other mantle rock in response to fluid flow. Pressures ≥2.2 GPa are consistent with stability of enstatite + aqueous fluid and of diopside + talc, with the occurrence of titanian chondrodite, and with the stability of garnet lherzolite. A chlorite separate has δ18O=6.9, consistent with mantle hydration. The small-scale reaction zones could have formed in a geologically brief time, plausibly just before eruption at about 25 Ma, and the responsible fluids probably also catalyzed recrystallization of associated eclogites. The hydration may have been restricted to shear zones that traversed the lower crust and the mantle to at least 75 km depth. The chlorite-rich rocks may be from the deepest part of the mantle that was sampled by the diatreme eruption. Chlorite-garnet pairs in garnet pyroxenites and pyrope megacrysts yield temperatures in the range 410–510° C. Low temperatures in the mantle of the Colorado Plateau are consistent with an unusually low mantle heat flux and with cooling of lithosphere by an underlying subducted slab. Received: 14 April 1994/Accepted: 23 December 1994  相似文献   

13.
Garnet-biotite gneisses, some of which contain sillimanite or hornblende, are widespread within the Otter Lake terrain, a portion of the Grenville Province of the Canadian Shield. The metamorphic grade is upper amphibolite to, locally, lower granulite facies. The atomic ratio Fe2+/(Fe2++ Fe3+) in biotite ranges from 0.79 to 0.89 (ferrous iron determinations in 10 highly pure separates), with a mean of 0.86. Mg and Fe2+ atoms occupy 67–78% of the octahedral sites, the remainder are occupied by Fe3+, Ti, and Al, and some are vacant. Mg/(Mg + Fe2+), denoted X, in the analysed samples ranges from 0.32 to 0.65. Garnet contains 1–24% grossular, 1–12% spessartine and X ranges from 0.07 to 0.34. Compositional variation in biotite and garnet is examined in relation to three mineral equilibria: (I) biotite + sillimanite + quartz = garnet + K-feldspar + H2O; (II) pyrope + annite = almandine + phlogopite; (III) anorthite = grossular + sillimanite + quartz. Measurements of X (biotite) and X (garnet) are used to construct an illustrative model for equilibrium (I) which relates the observed variation in X to a temperature range of 70°C or a range in H2O activity of 0.6; the latter interpretation is preferred. In sillimanite-free gneisses, the distribution of Mg and Fe2+ between garnet (low in Ca and Mn) and biotite is adequately described by a distribution coefficient (KD) of 4.1 (equilibrium II). The observed increase in the distribution coefficient with increasing Ca in garnet is ln KD= 1.3 + 2.5 × 10?2 [Ca] where [Ca] = 100 Ca/(Mg + Fe2++ Mn + Ca). The distribution coefficient is apparently unaffected by the presence of up to 12% spessartine in garnet. In several specimens of garnet-sillimanite-plagioclase gneiss, the Ca contents of garnet and of plagioclase increase in unison, as required by equilibrium (III). The mean pressure calculated from these data (n= 17) is 5.9 kbar, and the 95% confidence limits are ±0.5 kbar.  相似文献   

14.
在中国东部皖北地区分布着新元古代镁铁质岩,其中一些碱性基性岩为金刚石的赋矿岩石。为了确定安徽栏杆金刚石矿区的石榴子石种类,对矿区内不同类型的石榴子石进行系统采样,测定了62件石榴子石微区化学成分。结果显示,安徽栏杆石榴子石矿物化学式A_3~(2+)B_2~(3+)(SiO_4)_3中的A组阳离子由Mg~(2+)、Fe~(2+)和Ca~(2+)离子占位,B主要由Al~(3+)、Fe~(3+)、Mn~(3+)和Cr~(3+)离子占位,三价阳离子主要为Al~(3+),二价阳离子主要为Ca~(2+),表明研究区石榴子石主要为钙铝-钙铁-镁铝石榴子石系列。在62个样品中,发现了超硅石榴子石。经过计算其形成的压力范围为12.1～12.8GPa,深度可达300km。  相似文献   

15.
 Amphiboles were synthesized from bulk compositions prepared along the join Ca1.8Mg5.2Si8O22(OH)2–Ca1.8Mg3Ga4Si6O22(OH)2 hydrothermally at 750–850 °C and 1.0–1.8 GPa, and along the join Ca2Mg5Si8O22F2–Ca2Mg3Ga4Si6O22F2, anhydrously at 1000 °C and 0.7 GPa to document how closely the tschermak-type substitution is obeyed in these analogues of aluminous amphiboles. Electron-microprobe analyses and Rietveld X-ray diffraction structure refinements were performed to determine cation site occupancies. The extent of Ga substitution was found to be limited in both joins, but with the fluorine series having about twice the Ga content (0.6 atoms per formula unit, apfu) of the hydroxyl-series amphiboles (0.3 apfu). The tschermak-type substitution was followed very closely in the hydroxyl series with essentially equal partitioning of Ga between tetrahedral and octahedral sites. The fluorine-series amphiboles deviated significantly from the tschermak-type substitution and, instead, appeared to follow a substitution that is close to a Ca-pargasite substitution of the type: [6]Ga3++2[4]Ga3++1/2[A] Ca2+ = [6]Mg2++2[4]Si4++1/2[A]□. Infrared spectroscopy revealed an inverse correlation between the intensity of the OH-stretching bands and the Ga content for the hydroxyl- and fluorine-series amphiboles. The direct correlation between the Ga and F content and inverse relationship between the Ga and OH content may be a general phenomenon present in other minerals and suggests, for example, that high F contents in titanite are controlled by the Al content of the host rock and that there may be similar direct Al–F correlations in tschermakitic amphiboles. Evidence for the possibility that Al (Ga) might substitute onto only a subset of the tetrahedral sites in tschermakitic amphiboles was sought but not observed in this study. Received: 5 March 2001 / Accepted: 31 July 2001  相似文献   

16.
Violet, non-pleochroic and greenish-blue, pleochroic chromium-substituted sapphirines were found in corundum-bearing spinel-websterite xenolites from the Yakutian kimberlite pipes Noyabrskaya (N) and Sludyanka (Sl), respectively. The crystallochemical formulae of sapphirine crystals from such xenolites were determined by EMP to be (Mg3.40Fe0.23Al3.25Cr0.16)[6] Al 1.00 [6] [O2/Al4.53Si1.47O18] (N) and (Mg2.53Fe0.55 Mn0.04Ti 0.03 4+ Al3.55Cr 0.08 3+ )[6]Al 1.00 [16] [O2/Al4.28Si1.73O18] (Sl). Single crystal spectra in the range 35000–6000 cm1- showed a slightly polarization dependent absorption edge near 3200 cm1- (N) or 30000 cm1- (Sl) and unpolarized bands at 25300 and 17300 cm1-, typical of spin-allowed transitions, derived from 4A2g→4T1g and 4A2g→4T2g, of Cr3+ in octahedral sites, with point symmetry C1, of the structure. Another weak band at 23000 cm?1 in the sapphirine-N spectra is attributed to low symmetry splitting of the excited 4T1 (F)-State of Cr3+. These assignments lead to crystal field parameters Dq=1730cm?1 and B= 685cm?1 of Cr3+ in sapphirine. Crystallochemical and spectroscopic arguments suggest that Cr3+ subsitutes for Al in the M(1) or M(8) sites of the sapphirine structure. In addition to Cr3+-transitions, spectra of Sl exhibit weak dd-bands of Fe2+ at 10000 and 7700 cm1-, which are unpolarized in consistency with the C1 site symmetry of the octahedra in the structure. Spectra of Sl show also prominent, broad bands (Δv1/2～-5000 cm1-) at 15000 and 11000 cm1-, which occur in E//Y(//b) and E//Z(//c=12°) only and exhibit an intensity ratio αY∶αz close to 1∶3. This result, the large half width, as well as band energy — MM distance considerations suggest that these bands originate from Fe2+[6]-Fe3+[6] charge-transfer transitions in wall octahedra M(1)M(2), M(6)M(7) etc., forming MM vectors of 30° with the c-axis. The lack of Fe2+-Fe3+ charge-transfer bands in sapphirine N might indicate a lower oxygen fugacity during the formation of the websterite from the Noyabrskaya pipe compared to that from the Sludyanka pipe.  相似文献   

17.
 The crystal chemical response of basalt clinopyroxene to increasing pressure was investigated by means of crystal-structure simulation (a procedure that enables modeling of the structural parameters of a clinopyroxene of known chemistry without requiring direct X-ray diffraction analysis) using available experimental chemical data. Pressure proved the main physical variable governing clinopyroxene behavior in a magmatic environment. The general internal consistency of the simulation data permitted construction of an empirical geobarometer based on the relationship of cell volume (Vc) vs M1-site volume (VM1). The straightforward geobarometric formulation in the absence of direct X-ray analysis is: P(kbar)=698.443+4.985⋅AlT−26.826⋅Fe2+ M1−3.764⋅Fe3+ +53.989⋅AlM1+3.948⋅Ti+14.651⋅Cr −700.431⋅Ca−666.629⋅Na−682.848⋅MgM2−691.138⋅Fe2+ M2−688.384⋅Mn−6.267⋅(MgM2)2−4.144⋅(Fe2+ M2 where: (Fe2+ M1⋅MgM2)/(Fe2+ M2⋅MgM1)=e**(0.238⋅R3++0.289⋅CNM−2.315), CNM=Ca+Na+Mn, and R3+=AlM1+Fe3++Ti+Cr, with cations in atoms per formula unit. The geobarometer reproduces experimental pressures within ±2 kbar (=1σ; max. dev. ≤5 kbar; N=29) in the range 0–24 kbar and is applicable to near-liquidus C2/c clinopyroxenes crystallized from basaltic melts in the absence of garnet (excepting high-Al2O3 basalts). It is therefore suitable for many natural clinopyroxenes occurring as mega- or phenocrysts or forming well-preserved cumulate pyroxenites. If the above restrictions are not wholly satisfied, the Vc vs VM1 plot can also be used qualitatively to deduce the relative pressure conditions of clinopyroxenes forming from similar batches of magma. The structural simulation of experimental data also provided insight into the influence of minor chemical changes of the parental magma on the crystal chemistry of clinopyroxene at high pressure. Within the considered compositional space at given P-T, a CaO and a SiO2 in the melt have opposite effects on M2- and T-site cation populations. As a result, under similar physical conditions, clinopyroxenes from higher-CaO or more undersaturated basalts have higher VM2, VT and Vc and lower VM1. For basalts with normal contents of Al2O3 (<18 wt %), variations of major elements in the melt do not reduce the accuracy of the geobarometer. Received: 3 April 1994 / Accepted: 23 December 1995  相似文献   

18.
Summary The stoichiometry of pyroxenes {viiiX2+ viY2+ ivZ4+ 2 O6} and garnets {xiiX2+ 3 viY3+ 2 ivZ4+ 3 O12} is re-evaluated by a theoretical crystal-chemical approach that takes into account natural phenomena that do not fit with conventional anhydrous stoichiometric mineralogy: the existence in eclogites of microinclusions of other minerals that may have been exsolved from previous supersilicic or subsilicic UHPM pyroxene or garnet. Different definitions of supersilicic and subsilicic are discussed and the one based on the ability to exsolve SiO2 and leave behind a stoichiometric pyroxene or garnet is recommended for general adoption. The SHAND system (S = Si et al.; H = H; A = Al et al.; N = Na et al.; D = divalents) for projecting multivariate chemical space involving 23 cations and 104 selected natural or potential mineral species on to two essential diagrams (SAND and SHND) is described in full for the first time. Numerous possible chemical exchanges are considered and justified with respect to known mineral phenomena such as cation vacancies, octahedral silicon or protonation. Several new potential end-members are presented, in particular “supersilipyx”, “supersiligar” and “subsiligar”. It is suggested that small quantities of these end-members can be incorporated into UHPM solid-solutions and lead to various exsolution phenomena during eclogite exhumation.  相似文献   

19.
In the present work, a combination of various techniques is utilized for the study of nano-mineralogy and -geochemistry of high-grade karst-type bauxite (Al-rich and Fe-depleted samples; Al2O3 ca. 80 wt.%) from the Parnassos-Ghiona mines located in Greece. Initial characterization using PXRD and electron microscopy in microscale and mesoscale (SEM-EDS including STEM mode), proved the presence of “Fe-Cr-Ti-containing diaspore”, anatase and minor rutile. The study by means of 57Fe Mössbauer spectroscopy, in correlation with magnetic susceptibility measurements and, complemented, with Synchrotron-based spectroscopies at the microscale (SR micro-XRF and micro-XANES/-EXAFS), indicated that Fe3+, in contrast to [6]Cr3+, is not exclusively a component of the diaspore structure. While Cr3 + substitutes Al3 + in octahedral sites of diaspore ([6]Cr3+ ↔ [6]Al3+), the electron microscopy in nanoscale (TEM-EDS & EELS) revealed that Fe exists in the form of peculiar Fe3+-bearing nanominerals (most likely maghemite-type phases) between 25 and 45 nm in size, in addition to the Fe3+ ions substituting Al3+ in the diaspore structure. Moreover, it was proven that TiO2 polymorph mineral nanoparticles, particularly rounded anatase mesocrystals and nanocrystals and individual needle-shaped rutiles, are dispersed into the diaspore matrix. Thus, diaspore in the studied bauxite concerns -in fact- a distinct Fe3+-Cr3+-AlOOH low-T authigenic phase, demonstrated for the first time in literature. On the other hand, the observed TiO2 mineral nanoparticles (formed, together with diaspore, during diagenesis) and Fe nanominerals (formed during epigenesis) were hitherto unknown not only for the allochthonous karst-type bauxite deposits of Greece, but also for the overall bauxite deposits, worldwide.  相似文献   

20.
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   

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