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1.
To explore mechanisms of B-incorporation in common chain silicates we have investigated synthetic diopside samples produced under boron-saturated conditions by 11B and 29Si magic-angle spinning (MAS) NMR and single-crystal NRA, FTIR, EMP and XRD/SREF techniques. Our samples contain 0.14-0.65 wt.% B2O3. NMR reveals that B is predominantly present in trigonal coordination in the clinopyroxene structure. This observation is supported by vibrational bands characteristic for B-O stretching in BO3 groups in the range 1250-1400 cm−1 in polarised single crystal FTIR-spectra. Single crystal structure refinements suggest that boron replaces Si at the T site. Combined, these results suggest that boron replacement for Si at the T-site leads to disruption of one of the T-O bonds of the nominal clinopyroxene structure resulting in replacement of SiO4 tetrahedra by BO3 groups. Our results show that high concentrations of boron can be incorporated in the nominally boron-free diopside. Elevated B-concentrations in the present calcic clinopyroxenes are accompanied by modifications of the diopside crystal structure involving the breaking of one T-O bond and simultaneous formation of vacancies at the octahedral M2 site. These structural modifications destabilize the structure and constitute thereby limiting factors for incorporating higher boron concentrations in diopside.  相似文献   

2.
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   

3.
A clinopyroxene suite from lherzolite inclusions associated with the Victorian (Australia) “Newer Volcanics” has been investigated with the aim of understanding the clinopyroxene crystal-chemical response to increasing temperature (e.g. a melting model and/or crystallization processes prevailing at high pressure). The M1 clinopyroxene polyhedron dominates the intracrystalline physical-chemical variations, essentially given by the triple substitution AlVIFe M1 2 Ti4+⇌Cr3+ Fe3+Mg M1 2+ corresponding to an increase in the volume of M1 with increasing Mg/Mg+Fe2+ (mg) for the clinopyroxene. A relative Ca2+ increase in M2 ensures the necessary charge balance. However, Na+ occupancy of M2 persists to the highest mg values, i.e. maximum thermal stability, where the volume of M2 is the largest due to Fe M2 2+ depletion. The variations of M1 and M2 volumes are greater than, and opposite to, the variations in the volume of T (tetrahedron) by factors of ca. 3 and 1.5, respectively. Inclusions with relatively low clinopyroxene content (Mt. Porndon specimens) show distinct intracrystalline variations, essentially reflecting lower AlVI, i.e. higher volume of M1, and implying a lower pressure regime compared to clinopyroxene-rich analogues (Mt. Leura specimens). The intracrystalline relationships of the Mt. Porndon clinopyroxene suggest that the host peridotite inclusions survived larger degree of mantle melting at shallower depths relative to the Leura analogues.  相似文献   

4.
Multiple linear regression analysis has been applied to the geometric and chemical variables in sodic plagioclases in order to determine their relative effects on individual T-O bond lengths in the Al1+xSi3?xO8 tetrahedral framework. Using data from crystal structure analyses of low and high albite, An16 and An28, and assuming that low albite is completely ordered, 1 $$\begin{gathered} {\text{T}} - {\text{O = 1}}{\text{.568}} + {\text{[(0}}{\text{.122) x (Al content of the T site)]}} \hfill \\ {\text{ }} - {\text{[(0}}{\text{.037) x (}}\Delta {\text{{\rm A}l}}_{{\text{br}}} )] + [0.063){\text{ x }}(\Sigma {\text{[}}q{\text{/(Na,Ca}} - {\text{O)}}^{\text{2}} ])] \hfill \\ {\text{ }} + {\text{[(0}}{\text{.029) x (}} - {\text{1/cosT}} - {\text{O}} - {\text{T)]}} \hfill \\ \end{gathered}$$ where the Al content of a particular tetrahedral (T) site can be estimated from empirically-derived determinative curves, where Δ Albr is a linkage factor to account for the Al content of adjacent tetrahedral sites, where the formal charge on the (Na1?xCax) atom is q=1+x, and where T-O-T is the inter-tetrahedral angle involving the T-O bond. For sodic plagioclases it is essential to know only the anorthite content and the 2Θ131-2Θ1¯31 spacing (CuK α radiation) in order to determine the independent variables in this equation and thus to evaluate the individual T-O distances. The 64 individual T-O distances predicted for the four sodic plagioclases by this equation agree well with the observed T-O bond lengths (σ=0.004 Å; r=0.994), and the method has been used by way of example to rationalize the T-O bond lengths in analcime (cf. Ferraris, Jones and Yerkess, 1972).  相似文献   

5.
Summary The crystal-chemistry of clinopyroxene from a suite of Sunda arc volcanic rocks was investigated by X-ray structure refinement and microprobe analysis. Relationships with clinopyroxene from volcanic rocks of the intraplate environment were highlighted.Sunda clinopyroxenes were distinguished into two groups. The first consists of clinopyroxene from SiO2-saturated rock types and crystal rim from SiO2-undersaturated rock types, the second of crystal core from SiO2-undersaturated rock types. The crystal chemical behaviour of the two groups differs significantly, mainly in the geometrical relationships between M2 and T sites. While in the first group M2-O3 and T-O3 bond lengths shorten and lengthen respectively due to Ca and AlIV increase, in the second group in which M2 site is almost fully coordinated by Ca, -O3 bond lengths are forced to lengthen in spite of low AlIV content, in order to mantain the local charge balance around the O3 oxygens.It is noteworthy that Sunda clinopyroxene shows strong analogies with that from basaltic rocks from the Ethiopian plateau and K-rich lavas from the Roman Province respectively, reflecting similarities between the composition and mineralogical assemblages of the host rocks, although they all came from different tectonic environments. A relationship between intracrystalline Mg-Fe 2+ disorder and the explosive character of the volcanism is demonstrated.
Kristallchemie von Klinopyroxenen aus Gesteinen des Vulkanbogens der Sunda-Inseln
Zusammenfassung Die Kristallchemie von Klinopyroxenen aus einer Serie von vulkanischen Gesteinen des Sunda-Bogens wurde mit Röntgen-Strukturverfeinerungen und Mikrosonden-analysen untersucht. Beziehungen zu Klinopyroxenen vulkanischer Gesteine aus intra-Plattenpositionen werden beleuchtet. Die Sunda-Klinopyroxene wurden in zwei Gruppen eingeteilt. Die erste umfaßt Klinopyroxene SiO2-gesättigter Gesteinstypen und Kristallsäume SiO2-untersättigter Gesteinstypen, die zweite Kristallkerne SiO2-untersättigter Gesteinstypen. Das kristallchemische Verhalten der beiden Gruppen unterscheidet sich beträchtlich, hauptsächlich in den geometrischen Beziehungen zwischen den M2 und T Positionen. Während in der ersten Gruppe die M2-O3 und T-O3 Bindungsldngen durch Zunahme von Ca und AlIV kleiner bzw. größer werden, sind in der zweiten Gruppe die T-O3 Bindungslängen trotz niedrigen AlIV Gehaltes zu einer Vergrößerung gezwungen, damit um die O3 Atome der lokale Ladungsausgleich erhalten bleibt.Es ist bemerkenswert, daß die Sunda-Klinopyroxene große Analogien zu denen aus basaltischen Gesteinen des Abessinischen Plateaus und aus K-reichen Laven sowohl der Römischen Provinz als auch des Westafrikanischen Grabens zeigen. Dies spiegelt Ähnlichkeiten zwischen Zusammensetzung und Mineralbestand der Muttergesteine wider, obwohl sie all aus tektonisch unterschiedlichen Positionen kommen.Eine Beziehung zwischen intrakristalliner Mg-Fe2+ Unordnung und dem explosiven Charakter des Vulkanismus wird aufgezeigt.
  相似文献   

6.
High-resolution 27Al MAS NMR spectra of natural leucite recorded at H 0=11.7T contain three resolvable resonances at 27Al δ i = 69.2, 64.7, and 61.0±0.5 ppm. These three resonances are assigned to the three inequivalent framework positions of leucite: T3, T2, and T1, respectively. Fitting the observed spectra yields a Si,Al distribution for leucite in which approximately one-half of the Al is in T1 and one-quarter in each of T2 and T3. This Si,Al distribution differs substantially from those obtained by previous workers using 29Si NMR spectroscopy and X-ray diffraction. New 29Si NMR spectra and revision of previously reported 29Si NMR peak assignments, however, make the 27Al and 29Si NMR results consistent. The 27Al δ i correlate linearly with the mean T-O-T′ bond angles of the average structure, which allows the peak assignments to be made. However, this correlation lies distinctly toward higher frequency and larger bond angles than correlations for Si,Al ordered aluminosilicates, suggesting that the mean T(Al)-O-T′(Si) bond angle for each site in leucite is smaller than the mean bond angle of the average structure, which is averaged over T(Al)-O-T′(Si) and T(Si)-OT′(Si,Al) angles.  相似文献   

7.
Chemical and structural data are reported for C2/c pyroxene phenocrysts collected from three potassic series (Group A: basanite-tephrite, Group B: tephrite-phonolitic tephrite, Group C: alkaline basalt-trachybasalt) of the Neogene alkaline volcanics (NAVs) in northeastern Turkey, in order to investigate the evolution of the magmatic plumbing system and the location of magma chamber(s) with crystallization conditions. The rock series hosting the clinopyroxene phenocrysts show generally porphyritic texture and have a variable phenocryst-rich nature (20–58%), with phenocryst assemblages characterized by cpx ± ol ± plag ± foid ± amp ± bio. The clinopyroxene phenocrysts can be chemically classified as Ti- and Fe3+-rich Al-diopsides for Groups A and B (AB-cpxs) and Ti- and Fe3+-poor Al-diopsides for Group C (C-cpxs). They have poorly variable composition, clustering in the diopside field. Structurally, the diopside groups have nearly similar a (ranging from 9.73 to 9.75 ?), V cell (437.2–440.9 ?3), and 〈beta〉 angle values (106.01°–106.23°), but some differences in polyhedral parameters and geometries of the AB-cpxs and C-cpxs have been observed. For example, the AB-cpxs are characterized by larger c (5.27–5.30 vs. 5.25–5.28 ?), V T (2.27–2.30 vs. 2.23–2.28 ?3), and V M2 (25.53–25.72 vs. 25.41–25.59 ?3) values and smaller b (8.87–8.88 vs. 8.88–8.91 ?) and V M1 (11.49–11.63 vs. 11.64–11.83 ?3) values with respect to the C-cpxs. In addition, the AB-cpxs show higher values of V M2/V M1 (2.20–2.23) due to large V M2 and small V M1 compared to the V M2/V M1 ratios of the C-cpxs (<2.19). Such differences in the crystal structure of the AB-cpxs and C-cpxs from the NAVs are partly related to different crystallization pressures, but mostly related to variation in melt composition and, possibly, the influence of other crystallizing mineral phases. In particular, R(M2-O1) and R(M1-O2) (i.e. bond lengths) differences in the clinopyroxenes of different groups support the presence of evolved host rocks with different alkaline character (i.e. silica-undersaturated Groups A–B and silica-saturated Group C). Based on the cpx-geothermobarometry, the crystallization pressures for the C-cpxs are lower than 4.5 kbars, but the AB-cpxs have relatively high-pressure values (5.6–10.6 kbars), suggesting that the AB-cpxs crystallized in higher pressure environments. The relatively higher crystallization temperatures of the AB-cpxs also indicate higher cooling rates. The P–T estimates suggest that the source regions of the clinopyroxene phenocrysts from the NAVs were crustal magma chambers in a closed plumbing system at a moderate- to low-pressure regime.  相似文献   

8.
X-ray crystal structure refinements and microprobe analyses of clinopyroxenes from two suites of spinel-peridotite nodules are compared for an understanding of the structural response to a decrease in Ca content. The kinking of the tetrahedral chain (O3-O3-O3 angle) of the C2/c structure associated with decreased Ca content shows behavior similar to that observed for the A-tetrahedral chain of the P21/c structure. Contemporaneously the occupancy of the M2′ split site increases. In addition, as a consequence of the low Ca content, the M2 polyhedron dominates the structural rearrangement of the clinopyroxenes considered here.  相似文献   

9.
A crystal chemical investigation of clinopyroxenes from a suite of nepheline-bearing lavas located in the Nyambeni Range of Kenya has delineated the polyhedral site configurations and related intracrystalline relationships. These are distinct from those determined for the clinopyroxene in an analogous suite of leucite-bearing lavas from the Sabatini volcanoes in the Roman Region of Italy (Dal Negro et al. 1985).The Nyambeni clinopyroxene, varying from salite to hedenbergite, preferentially accepts Na in the M2 site to balance increasing Fe2+ and Si, respectively, whereas the Sabatini clinopyroxene is confined within the salite field and preferentially accepts Aliv to balance the effect of increasing (Fe3++Ti4++Alvi+Cr3+)M1.The Fe2+/Fe3+ and K/Na ratios of the host rocks emerge as significant factors in determining the different polyhedral configurations and evolutions of the clinopyroxene from the two lava suites, respectively. The resulting Mg-Fe2+ order-disorder relationships in M1–M2 are also distinct in the two clinopyroxenes. A high degree of MgFe2+ order in M1–M2 corresponds to the largest configurational, hence energetic, difference between M1 and M2 in the Nyambeni clinopyroxene, whereas the converse applies to the Sabatini clinopyroxene.In view of the significant crystal chemical differences and distinct evolution trends, it is proposed that salites from alkali volcanic rocks may be referred to as Nyambeni-type or Sabatini-type, respectively.  相似文献   

10.
Summary The clinopyroxene suites from lherzolite nodules from Mts. Leura and Noorat (Victoria, Australia) have been investigated by X-ray diffraction and electron probe microanalyses (Dal Negro et al., 1984; Cundari et al., 1986).The evolution of the host nodule is shown by general depletion of AlIv, AVI, Ti4+, Fe2+ and enrichment of Si, Mgm,, Fe3+, Cr3+, Ca, while Na depletion occurs only in the clinopyroxenes from Mt. Noorat. Different mechanisms of cation substitution are thus involved in the two clinopyroxene suites, suggesting different total pressures of equilibration in the stability field of spinel.Modifications involving the M1 octahedron are mainly ascribed to variable amounts of trivalent cations, the volume of the M 1 site increasing with decreasing content of trivalent cations in each suite. The differences in M 1 site configuration between the Mt. Leura and Mt. Noorat clinopyroxene suites are ascribed to the different amounts of A1v1 and FeM,.The volume of the T tetrahedral site is generally related to A1Iv in each suite. An increase in T site volume from Mt. Leura to Mt. Noorat clinopyroxenes was found however, due to lengthening of the T-Obrg bond lengths, for similar AIIv contents. The volume of the M2 site, generally related to Ca content, was generally higher in the Noorat clinopyroxenes for similar Ca (and Ca + Na) contents, due to the longer M2-O3C1 bond length, strongly related to Na content. Cell volume is linearly correlated to M 1 volume in each suite, but is definitely higher in the Noorat clinopyroxenes for similar M 1 volume. All the structural data show that the total pressure of equilibration in the Noorat clinopyroxenes was lower than that in the Leura clinopyroxenes, as suggested by chemical data.
Die Kristallchemie von hochdruck-klinopyroxenen aus spinell-lherzolithknollen von Mt. Leura und Mt. Noorat, Victoria, Australien
Zusammenfassung Die Klinopyroxenparagenesen aus Lherzolitheinschlüssen von Mt. Leura und Mt. Noorat (Victoria, Australien) wurden mittels Röntgendiffraktometrie und Elektronenmikrosonde untersucht (Dal Negro et al., 1984; Cundari et al., 1986). Die Lherzolitheinschlüsse zeigen generell eine Abnahme von AlIV, AlVI, Ti4+, Fe MI 2+ und eine Zunahme von Si, Mgm,, Fe3+, Cr3+ und Ca. Eine Abnahme von Na tritt nur in Klinopyroxenen von Mt. Noorat auf. Verschiedene Substitutions-Mechanismen der Kationen weisen auf verschiedene Equilibrationsdrucke im Stabilitätsbereich der Spinelle hin und sind daher in den beiden Klinopyroxenserien zu berücksichtigen. Modifikationen in der oktaedrischen M1-Position wurden vor allem dem wechselnden Anteil an dreiwertigen Kationen zugeschrieben, wobei in jeder der beiden Serien das Volumen der Ml-Position mit abnehmenden Gehalten dreiwertiger Kationen zunimmt. Die unterschiedliche Konfiguration der M1-Position der Klinopyroxene von Mt. Leura und Mt. Noorat wird mit unterschiedlichen Gehalten an AlVI und Fe MI 2+ , in Zusammenhang gebracht.Das Volumen der tetraedrischen T-Position ist normalerweise mit den Gehalten an AllIV in jeder Serie verknüpft. Ein Vergleich der Klinopyroxene von Mt. Leura und Mt. Noorat zeigte jedoch, daß bei gleichen Gehalten an AlVI das Volumen der tetraedrischen Position infolge einer Aufwertung der T-Obrg.-Bindungen zunimmt. Das Volumen der M2-Position, üblicherweise mit dem Ca-Gehalt korreliert, ist in den Klinopyroxenen von Mt. Noorat bei ähnlichen Ca (und Ca f Na) Gehalten infolge größerer M2--O3C1-Abstände größer. Sie stehen also mit den Na-Gehalten in Verbindung.Das Volumen der Elementarzelle korreliert mit dem der M1-Position in jeder Serie; es ist aber in den Klinopyroxenen von Mt. Noorat deutlich höher. Die Ergebnisse der Strukturuntersuchungen zeigen-wie auch die chemischen Daten-, daß die genannten Equilibrationsdrucke für die Klinopyroxene von Mt. Noorat niedriger waren als für die von Mt. Leura.

With 2 Figures  相似文献   

11.
Comparison of polarized optical absorption spectra of natural Ca-rich diopsides and synthetic NaCrSi2O6 and LiCrSi2O6 clinopyroxenes, evidences as vivid similarities, as noticeable differences. The similarities reflect the fact that in all cases Cr3+ enters the small octahedral M1-site of the clinopyroxene structure. The differences are due to some iron content in the natural samples causing broad intense near infrared bands of electronic spin-allowed dd transitions of Fe2+(M1, M2) and intervalence Fe2+/Fe3+ charge-transfer transition, and by different symmetry and different local crystal fields strength of Cr3+ in the crystal structures. The positions of the spin-allowed bands of Cr3+, especially of the low energy one caused by the electronic 4 A 2g → 2 T 1g transition, are found to be in accordance with mean M1–O distances. The local relaxation parameter ε calculated for limCr 3+ → 0 from the spectra and interatomic á Cr - O ñ \left\langle {Cr - O} \right\rangle and á Mg - O ñ \left\langle {Mg - O} \right\rangle distances yields a very high value, 0.96, indicating that in the clinopyroxene structure the local lattice relaxation around the “guest” ion, Cr3+, deviates greatly from the “diffraction” value, ε = 0, than in any other known Cr3+-bearing systems studied so far. Under pressure the spin-allowed bands of Cr3+ shift to higher energies and decrease in intensity quite in accordance with the crystal field theoretical expectations, while the spin-forbidden absorption lines remain practically unshifted, but also undergo a strong weakening. There is no evident dependence of the Racah parameter B of Cr3+ reflecting the covalence of the oxygen-chromium bond under pressure: within the uncertainty of determination it may be regarded as practically constant. The values of CrO6 octahedral modulus, k\textpoly\textloc k_{\text{poly}}^{\text{loc}} , derived from high-pressure spectra of natural chromium diopside and synthetic NaCrSi2O6 kosmochlor are very close, ~203 and ~196 GPa, respectively, being, however, nearly twice higher than that of MgO6 octahedron in diopside, 105(4) GPa, obtained by Thompson and Downs (2008). Such a strong stiffening of the structural octahedron, i.e. twice higher value of k\textCr3 + \textloc k_{{{\text{Cr}}^{3 + } }}^{\text{loc}} comparing with that of k\textMg2 + \textloc k_{{{\text{Mg}}^{2 + } }}^{\text{loc}} , may be caused by simultaneous substitution of Ca2+ by larger Na+ in the neighboring M2 sites at so-called jadeite-coupled substitution Mg2+ + Ca2+ → Cr3+ + Na+. It is also remarkable that the values of CrO6 octahedral modulus of NaCrSi2O6 kosmochlor obtained here are nearly twice larger than that of 90(16) GPa, evaluated by high-pressure X-ray structural refinement by Origlieri et al. (2003). Taking into account that the overall compressibility of the clinopyroxene structure should mainly be due to the compressibility of M1- and M2-sites, our k\textCr3 + \textloc k_{{{\text{Cr}}^{3 + } }}^{\text{loc}} -value, ~196 GPa, looks much more consistent with the bulk modulus value, 134(1) GPa.  相似文献   

12.
Carbonation and decarbonation of eclogites: the role of garnet   总被引：3，自引：0，他引：3  
Carbonates are potentially significant hosts for primordial and subducted carbon in the Earth's mantle. In addition, the coexistence of carbonate with silicates and reduced carbon (diamond or graphite), allows constraints to be placed on the oxidation state of the mantle. Carbonate-silicate-vapor reactions control how carbonate + silicate assemblages may form from carbon-bearing vapor + silicate assemblages with increasing pressure. In olivine-bearing rocks such as peridotite, considered the dominant rock type in the upper mantle, the lowest-pressure carbonate-forming reactions involve olivine (±clinopyroxene) reacting with CO2 (e.g., Wyllie et al. 1983). In eclogitic rocks, the essential mineral assemblage is omphacitic clinopyroxene + garnet, without olivine. Therefore, alternative carbonate-forming reactions must be sought. The carbonation of clinopyroxene via the reaction dolomite + 2 coesite = diopside + 2 CO2 was studied experimentally by Luth (1995). The alternative possibility that garnet reacts with CO2 is explored here by determining the location of the reaction 3 magnesite + kyanite + 2 coesite = pyrope + 3 CO2 between 5 and 11 GPa in multi-anvil apparatus. At the temperatures ≥1200 °C, carbonation of eclogitic rocks with increasing pressure will proceed initially by reaction with clinopyroxene, because the pyrope-carbonation reaction lies at higher pressures for a given temperature than does the diopside-carbonation reaction. Diluting the pyrope component of garnet and the diopside component of clinopyroxene to levels appropriate for mantle eclogites does not change this conclusion. At lower temperatures, appropriate for “cold” slabs, it is possible that the converse situation will hold, with initial carbonation proceeding via reaction with garnet, but this possibility awaits experimental confirmation. Decarbonation of an eclogite under “normal mantle” geothermal conditions by a decrease in pressure, as in an ascending limb of a mantle convection cell, would be governed by the formation of clinopyroxene + CO2. At higher pressure than this reaction, any CO2 produced by the breakdown of magnesite reacting with kyanite and coesite would react with clinopyroxene to produce dolomite + coesite. Release of CO2 from eclogite into mantle peridotite would form carbonate at sub-solidus conditions and produce a dolomitic carbonate melt if temperatures are above the peridotite-CO2 solidus. Received: 4 May 1998 / Accepted: 23 December 1998  相似文献   

13.
Diamonds and eclogites of the Jericho kimberlite (Northern Canada)   总被引：1，自引：1，他引：0  
We studied diamonds and barren and diamondiferous eclogite xenoliths from the Jericho kimberlite (Northern Slave craton). The majority of the diamonds are non-resorbed octahedral crystals, with moderately aggregated N (IaB < 50%, N < 300 ppm) and δ13C = −5 to −41‰. The diamonds belong to “eclogitic” (90% of the studied samples), “websteritic” (7%) and “peridotitic” (3%) assemblages. The Jericho diamonds differ from the majority of “eclogitic” diamonds worldwide in magnesian compositions of associated minerals and extremely light C isotopic compositions (δ13C = −24 to −41‰). We propose that metasomatism triggered by H2O fluids may have been involved in the diamond formation. Multiple episodes of the metasomatism and associated melt extraction of various ages are evident in Jericho eclogite xenoliths where primary garnet and clinopyroxene have been recrystallized to more magnesian minerals with higher contents of some incompatible trace elements and to hydrous secondary phases. The model is supported by the general similarity of mineral compositions in diamondiferous eclogites to those in diamond inclusions and to secondary magnesian garnet and clinopyroxene in recrystallized barren eclogites. The ultimate products of the metasomatism could be “websteritic” diamond assemblages sourced from magnesian eclogites. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

14.
Summary The crystal structures of 20 natural diopsides have been refined. For some samples, microprobe analyses show a Si deficiency in the tetrahedron with no A1 present; this suggests that some Ti4+ may enter the tetrahedral site. Geometrical variations in these samples with respect to the others are discussed in the light of this Si Ti4+ substitution. The volumes of their M1 sites are larger because of the absence of R3+ cations, the octahedron being very regular; in the same way, the volumes of M2 sites of these samples are greater not because of different site occupancies but because of significant charge modifications around the O3 and O1 oxygens, caused by the tetrahedral site. The low distortion of M1 site and the lengthening of (M2-O1) and M2-O3 bond lengths are a clue to the presence of small amounts of Ti at the tetrahedral site.
Kristallchemische untersuchung natürlicher diopside: Geometrische hinweise für tetraedrische Si-Ti substitution
Zusammenfassung Die Kristallstrukturen von zwanzig natürlichen Diopsiden sind verfeinert worden. In einigen Proben zeigen Mikrosondenanalysen zu geringe Si-Werte im Tetraeder ohne daß A1 anwesend wäre. Dies weist darauf hin, daß Ti4+ Tetraederplätze einnehmen könnte. Geometrische Variationen in diesen Proben werden im Lichte der genannten Substitution diskutiert. Die Volumen von M1-Plätzen sind größer wegen der Abwesenheit von R3+ Kationen, wobei das Oktaeder sehr gleichmäßig ist. Die Volumina von M2-Plätzen sind noch größer nicht wegen verschiedener Besetzungen dieser Plätze sondern wegen signifikanter Ladungsmodifikationen im Bereich von O3 und O1 Sauerstoffen, die durch die tetraedrische Position bewirkt wird. Die geringe Distortion der M1-Plätze und die Verlängerung der (M2-O1) und (M2-O3) Abstände weisen auf die Anwesenheit von geringen Titangehalten auf Tetraederplätzen hin.
  相似文献   

15.
傅平秋  李哲 《矿物学报》1996,16(2):147-151
本文使用穆斯堡尔效应研究了在高温高压下合成的铁橄榄石和铁尖晶橄榄石。２９８Ｋ温度下铁橄榄石的穆斯堡尔谱由一组双峰组成，它被指派给Ｆｅ＾２＋（Ｍ１，Ｍ２）离子。２９８Ｋ温度下铁尖晶橄榄石的穆斯堡尔谱由三组双峰组成，其中两组双峰指派给八面体位置Ｂ上的Ｆｅ＾２＋，另一组双峰归为四面体位置Ａ上的Ｆｅ＾３＋，两组Ｆｅ＾２＋双峰的同质异能迁移近似相等而四极分裂不同，Ｓｉ原子在八面体位置上的占有率为６％～１０％  相似文献   

16.
The effects of low-temperature on the crystal structure of a natural epidote [Ca1.925Fe0.745Al2.265Ti0.004Si3.037O12(OH), a = 8.8924(7), b = 5.6214(3), c = 10.1547(6)? and β = 115.396(8)° at room conditions, Sp. Gr. P21 /m] have been investigated with a series of structure refinements down to 100 K on the basis of X-ray single-crystal diffraction data. The reflection conditions confirm that the space group is maintained within the T-range investigated. Structural refinements at all temperatures show the presence of Fe3+ at the octahedral M(3) site only [%Fe(M3) = 70.6(4)% at 295 K]. Only one independent proton site was located and two possible H-bonds occur, with O(10) as donor and O(4) and O(2) as acceptors. The H-bonding scheme is maintained down to 100 K and is supported by single crystal room-T polarised FTIR data. FTIR Spectra over the region 4,000–2,500 cm−1 are dominated by the presence of a strongly pleochroic absorption feature which can be assigned to protonation of O(10)–O(4). Previously unobserved splitting of this absorption features is consistent with a NNN influence due to the presence of Al and Fe3+ on the nearby M(3) site. An additional relatively minor absorption feature in FTIR spectra can be tentatively assigned to protonation of O(10)–O(2). Low-T does not affect significantly the tetrahedral and octahedral bond distances and angles, even when distances are corrected for “rigid body motions”. A more significant effect is observed for the bond distances of the distorted Ca(1)- and Ca(2)-polyhedra, especially when corrected for “non-correlated motion”. The main low-T effect is observed on the vibrational regime of the atomic sites, and in particular for the two Ca-sites. A significant reduction of the magnitude of the thermal displacement ellipsoids, with a variation of U eq (defined as one-third of the trace of the orthogonalised U ij tensor) by ~40% is observed for the Ca-sites between 295 and 100 K. Within the same T-range, the U eq of the octahedral and oxygen sites decrease similarly by ~35%, whereas those of the tetrahedral cations by ~22%.  相似文献   

17.
Quaternary basalts in the Cerro del Fraile area contain two types of mantle xenoliths; coarse-grained (2–5 mm) C-type spinel harzburgites and lherzolites, and fine-grained (0.5–2 mm) intensely metasomatized F-type spinel lherzolites. C-type xenoliths have high Mg in olivine (Fo = 90–91) and a range in Cr# [Cr/ (Cr + Al) = 0.17–0.34] in spinel. Two C-type samples contain websterite veinlets and solidified patches of melt that is now composed of minute quenched grains of plagioclase + Cr-spinel + clinopyroxene + olivine. These patches of quenched melts are formed by decompression melting of pargasitic amphibole. High Ti contents and common occurrence of relic Cr-spinel in the quenched melts indicate that the amphibole is formed from spinel by interaction with the Ti-rich parental magma of the websterite veinlets. The fO2 values of these two C-type xenoliths range from ΔFMQ −0.2 to −0.4, which is consistent with their metasomatism by an asthenospheric mantle-derived melt. The rest of the C-type samples are free of “melt,” but show cryptic metasomatism by slab-derived aqueous fluids, which produced high concentrations of fluid-mobile elements in clinopyroxenes, and higher fO2 ranging from ΔFMQ +0.1 to +0.3. F-type lherzolites are intensely metasomatized to form spinel with low Cr# (∼0.13) and silicate minerals with low MgO, olivine (Fo = ∼84), orthpyroxene [Mg# = Mg/(Mg + ΣFe) = ∼0.86] and clinopyroxene (Mg# = ∼0.88). Patches of “melt” are common in all F-type samples and their compositions are similar to pargasitic amphibole with low TiO2 (<0.56 wt%), Cr2O3 (<0.55 wt%) and MgO (<16.3 wt%). Low Mg# values of silicate minerals, including the amphibole, suggest that the metasomatic agent is most likely a slab melt. This is supported by high ratios of Sr/Y and light rare earth elements (REE)/heavy REE in clinopyroxenes. F-type xenoliths show relatively low fO2 (ΔFMQ −0.9 to −1.1) compared to C-type xenoliths and this is explained by the fusion of organic-rich sediments overlying the slab during the slab melt. Trench-fill sediments in the area are high in organic matter. The fusion of such wet sediments likely produced CH4-rich fluids and reduced melts that mixed with the slab melt. High U and Th in bulk rocks and clinopyroxene in F-type xenoliths support the proposed interpretation.  相似文献   

18.
Babingtonite, Ca2Fe2+Fe3+[Si5O14(OH)] (Z?=?2, space group $ P\overline{1} $ ) from Yakuki mine (Japan), Grönsjöberget (Sweden), Kandivali Quarry (India), Baveno Quarry (Italy), Bråstad Mine (Norway), and Kouragahana (Japan), and manganbabingtonite, Ca2(Mn2+, Fe2+)Fe3+[Si5O14(OH)], from Iron Cap mine (USA) were studied using electron-microprobe analysis (EMPA), 57Fe Mössbauer analysis and single-crystal X-ray diffraction methods to determine the cation distribution at M1 and M2 and to analyze its effect on the crystal structure of babingtonite. Although all studied babingtonite crystals are relatively homogeneous, chemical zonation due to mainly Fe ? Mn substitution is observed in manganbabingtonite. Mössbauer spectra consist of two doublets with isomer shift (I.S.)?=?1.16–1.22 mm/s and quadrupole splitting (Q.S.)?=?2.33–2.50 mm/s and with I.S.?=?0.38–0.42 mm/s and Q.S.?=?0.82–0.90 mm/s, assigned to Fe2+ and Fe3+ at the M1 and M2 octahedral sites, respectively. The determined ratio of Fe2+/total Fe in manganbabingtonite (0.26) was smaller than that in the others (0.35–0.44) because of high Mn2+ content instead of Fe2+. The unit-cell parameters of babingtonite are a?=?7.466–7.478, b?=?11.624–11.642, c?=?6.681–6.690 Å, α?=?91.53–91.59, β?=?93.86–93.94, γ?=?104.20–104.34º, and V?=?560.2–562.3 Å3, and those of manganbabingtonite are a?=?7.4967(3), b?=?11.6632(4), c?=?6.7014(2) Å, α?=?91.602(2), β?=?93.989(2), γ?=?104.574(3)º, and V =565.09(5) Å3. Structural refinements converged to R 1 values of 1.64–3.16 %. The <M1-O> distance was lengthened due to the substitution of large octahedral cations such as Mn2+ for Fe2+. The increase of the M1-O8, M1-O8’ and M1-O13 lengths with mean ionic radii is slightly more pronounced than of the other M1-Oi lengths. The lengthened M1-O13 distance leads the positive correlation between Si5-O15-Si1 angle and M1-O13 distance. The increase of Si2-O3-Si1 and Si5-O12-Si4 angles due to the increase of mean ionic radius of M2 is also observed.  相似文献   

19.
Summary ?Results of experimental investigations in the dry system PtS-PdS-NiS at 1100°C, 1000°C, and 900°C are presented. The phases observed at 1100°C are “cooperite” and a melt, at 1000°C “cooperite”, “braggite”, and a melt and at 900°C “cooperite”, “braggite”, “vysotskite”, Ni1−xS, and a melt. At 1100°C the maximum solubility of Ni in ideal, Pd-free “cooperite” is 2.7 atomic per cent and the Pd-content limit in Ni-free “cooperite” is 12.8 atomic per cent. At 1000°C the maximum solubility of Ni in ideal, Pd-free “cooperite” is 3.3 atomic per cent and the Pd-content in Ni-free “cooperite” is 13.7 atomic per cent. The “braggite” composition ranges from Pt0.56Pd0.38Ni0.06S and Pt0.59Pd0.41S in a Ni-saturated and Ni-free environment respectively to Pt0.18Pd0.80Ni0.02S and Pt0.14Pd0.86S respectively. At 900°C the maximum Ni-content in ideal Pd-free “cooperite” is 3.1 atomic per cent and the Pd-limit in Ni-free “cooperite” is 12.5 atomic per cent. The “braggite” composition ranges from Pt0.59Pd0.29Ni0.12S and Pt0.60Pd0.40S for a Ni-saturated and Ni-free environment respectively, to Pd0.91Ni0.09S and PdS respectively. The Ni-content in “braggite” and “vysotskite” increases slightly with increasing Pt/Pd ratios and is higher at 900°C than at 1000°C. Comparison of experimental trends with cooperite, braggite, and vysotskite analyses from the literature implies high temperatures of formation for Pt-Pd-Ni sulphides in placers if Ni-saturation is assumed.
Zusammenfassung ?Synthetischer ,,Cooperit”, ,,Braggit” und “Vysotskit” im System PtS-PdS-NiS bei 1100°C, 1000°C und 900°C Ergebnisse experimenteller Untersuchungen im trockenen System PtS-PdS-NiS bei 1100°C, 1000°C und 900°C werden dargestellt. Bei 1100°C sind die Phasen “Cooperit” und Schmelze, bei 1000°C “Cooperit”, “Braggit” und Schmelze und bei 900°C “Cooperit”, “Braggit”, “Vysotskit”, Ni1−xS und Schmelze stabil. Bei 1100°C ist die maximale L?slichkeit von Ni in idealem, Pd-freiem “Cooperit” 2.7 Atomprozent und der Pd-Gehalt in Ni-freien “Cooperit” liegt bei maximal 12.8 Atomprozent. Bei 1000°C ist die maximale L?slichkeit von Ni in idealem, Pd-freien “Cooperit” 3.3 Atomprozent und der Pd-Gehalt in Ni-freien “Cooperit” liegt bei maximal 13.7 Atomprozent. Die Zusammensetzung des “Braggits” variiert zwischen Pt0.56Pd0.38Ni0.06S und Pt0.18Pd0.80Ni0.02S in einem Ni-ges?ttigtem und zwischen Pt0.59Pd0.41S und Pt0.14Pd0.86S in einem Ni-freien Umfeld. Bei 900°C liegt die maximale L?slichkeit von Ni in idealem Pd-freien “Cooperit” bei 3.1 Atomprozent und der Pd-Gehalt in Ni-freien “Cooperit” liegt bei maximal 12.5 Atomprozent. Die Zusammensetzung des “Braggits” variiert zwischen Pt0.59Pd0.29Ni0.12S und Pd0.89Ni0.08S in einem Ni-ges?ttigten und zwischen Pt0.59Pd0.40S und PdS in einem Ni-freien Umfeld. Der Nickelgehalt in “Braggit” und “Vysotskit” nimmt mit zunehmendem Pt/Pd Verh?ltnis zu und ist bei 900°C h?her als bei 1000°C. Ein Vergleich der experimentellen Trends mit Cooperit, Braggit und Vysotskit Analysen aus der Literatur weist auf eine Hochtemperaturbildung der Pt-Pd-Ni Sulfide in Seifenlagerst?tten hin, wenn man von Nickels?ttigung ausgeht.

Received October 1, 1998;/revised version accepted September 7, 1999  相似文献   

20.
Entropies of Al-Si in layer silicates have been calculated using a series of CVM approximations for the honeycomb lattice. The parameters of the models have been constrained by 29Si NMR data. The results of low order approximations such as “pair” and “star” have been rejected because of their low accuracy at high Al/(Al+Si) ratios. Reasonably accurate results have been achieved with the help of the “hexagon” and “star-hexagon” approximations. Received: 31 October 1997 / Revised, accepted: 17 April 1998  相似文献   

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