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1.
2.
A. Gloter J. Ingrin D. Bouchet K. Scrivener C. Colliex 《Physics and Chemistry of Minerals》2000,27(7):504-513
Observations by transmission electron microscopy (TEM) of the submicrometer phases present in calcium aluminate cements have
shown that Ca-Al-Fe oxides coexist in two forms with brownmillerite (b) and perovskite (p) structures, respectively. Homogeneous
single crystals of both brownmillerite and perovskite have been observed but exsolved lamellae also occur on the scale of
tens of nanometers. Perovskite lamellae in brownmillerite exhibit coherent interfaces with an almost perfect [1 0 1]b = {1 0 0}p topotactic relationship. Energy-dispersive X-ray spectroscopy (EDXS) measurements show that perovskite lamellae are enriched
in Ti and Si relative to the brownmillerite lamellae. The perovskite phase may accommodate up to 0.17 Si atoms per formula
unit, but the exsolution process seems mainly to concern the Ti content. It is estimated that the solvus width ranges between
concentrations of 0.06 < Ti < 0.13 atoms per formula unit. O K and Fe L
2,3 edges collected by electron energy loss spectrometry (EELS) confirm that both phases are mainly composed of Fe3+, requiring that the perovskite is highly oxygen-deficient. Al K and Si K EELS spectra have features comparable with those of fourfold-co-ordinated Al and Si sites, suggesting that they are probably
located close to oxygen-vacant sites.
Received: 23 June 1999 / Accepted: 18 February 2000 相似文献
3.
Sherif Kharbish 《Physics and Chemistry of Minerals》2007,34(8):551-558
A Raman spectroscopic study of Fe-rich sphalerite (Zn1 − x
Fe
x
S) has been carried out for six samples with 0.10 ≤ x ≤ 0.24. Both the intensities and frequencies of the TO and LO modes of sphalerite are approximately independent of Fe concentration.
However, the substitution of Zn by Fe results in five additional bands with frequencies between the TO (271 cm−1) and LO (350 cm−1) modes. Three of these bands are attributed to resonance modes (i.e. Y
1, Y
2 and Y
3 modes). The fourth band (B mode) is assigned to a breathing mode of the nearest-neighbor sulfur atoms around the Fe atoms.
The band at 337 cm−1 is attributed to the presence of Fe3+. The excellent correlations between the normalized intensities of these five different modes and x
Fe
show that these modes depend on Fe-content. Another extra mode at 287 cm−1 is assigned to the presence of Cd in sphalerite. 相似文献
4.
Synchrotron radiation S K-edge XANES spectra and unit-cell parameters are used to investigate the local electronic structure
of non-stoichiometric binary and ternary Fe-Co-Ni monosulfide solid solution (mss; M0.923S, M = Fe, Co, Ni) quenched from 800 °C and low pressure. The prominent absorption edge feature of the XANES spectra represents
transition of S 1s core level electrons to unoccupied S 3p σ* antibonding orbitals hybridized with empty metal 3d(eg) orbitals. There is a progressive increase in area of the edge peak from Fe0.923S to Ni0.923S and Co0.923S, which correlates with progressive decrease in c and a parameters for the NiAs-type subcell and increase in metallic character, and reflects increase in the number and availability
of empty eg
β orbitals and covalence of metal-S bonds. More generally, the area of the edge peak exhibits an inverse linear correlation
with a, c and unit-cell volume of binary and ternary mss. This inverse linear correlation is attributed to progressive increase in
covalence and M-S-M bonding interaction in the c-axis direction, through metal-S [M 3d(eg) - S 3p (or 3d)] π bonding. However, the area of the edge peak does not correlate very well with the average number of 3d
electrons per metal atom in these solid solutions, showing that the absorption of synchrotron radiation reflects the local
electronic structure of individual absorber atoms (i.e. the SM6 cluster), and is not a group (crystal energy band) effect.
Received: 21 March 2000 / Accepted: 14 July 2000 相似文献
5.
Low-temperature single-crystal Raman spectrum of pyrope 总被引:1,自引:1,他引:0
The single-crystal polarized Raman spectra of synthetic pyrope, Mg3Al2Si3O12, were measured at room temperature and 5 K, as were the room-temperature unpolarized spectra of two natural pyrope-rich crystals.
No major differences in the spectra between room temperature and 5 K are observed or are present between the synthetic and
the natural crystals. The spectra are consistent with the proposal that the Mg cation is dynamically disordered and not statically
distributed over subsites in the large triangular-dodecahedral E-site in pyrope. A low-energy band at about 135 cm−1 softens and shows a large decrease in its line width with decreasing temperature. The presence of a weak, broad band at about
280 cm−1 may be due to anharmonic effects, as could the one at 135 cm−1. The latter is assigned to the rattling motion of Mg in pyrope in the plane of the longer Mg-O(4) bonds (Kolesov and Geiger
1998). The successful modeling of the anisotropic motion of the Mg cation in pyrope, which has an anharmonic character, provides
a valuable test of the validity of empirical or semi-empirical lattice-dynamic calculations for silicates.
Received: 10 May 1999 / Accepted: 10 April 2000 相似文献
6.
H. Graetsch 《Physics and Chemistry of Minerals》2001,28(5):313-321
The crystal structure of intermediate incommensurate tridymite was refined at 150 °C from powder data. Upon cooling from
above 220 °C, the basic structure with space group symmetry C2221 is gradually distorted from orthorhombic to monoclinic symmetry. With decreasing temperature, the monoclinic angle γ smoothly
opens up to 90.3°, while a displacive modulation with temperature-dependent wavelength develops. The 3 + 1 dimensional superspace
group of the incommensurate phase is C1121(αβ0). The modulation mainly consists of two sinusoidal transverse displacement waves for the silicon atoms coupled to rotations
of the rigid SiO4/2 tetrahedra. The wave vector is r=0.1192(1)a* − 0.0043(1)b* at 150 °C. Below 150 °C tridymite discontinuously transforms to another orthorhombic phase and the modulation partially
locks in at the wave vector r
1=1/3a*. Simultaneously, an additional incommensurate modulation with r
2= 0.0395(1)b* − 0.3882(1)c* is formed. The two-dimensional modulation does not vary significantly with the temperature.
Received: 13 September 2000 / Accepted: 29 January 2001 相似文献
7.
Grain growth kinetics in CaTiO3-perovskite + FeO-wüstite aggregates were studied at the conditions of T = 1223–1623 K, P = 0.1 MPa and P = 200 MPa. Starting samples were fabricated by hot-pressing mechanically mixed powders of CaTiO3 + FeO with FeO = 0%, 1%, 3%, 6%, 10%, 20% and 100% by weight in a gas-medium apparatus at 1323 K and 300 MPa for 5 h. The
increase of grain size (G) of CaTiO3 with time (t) follows a growth law: G
n
−G
n
0 = κ·t(κ=κ0exp(−(Q/RT)). Two grain growth regimes are observed at T < 1523 K and T ≥ 1523 K. For T < 1523 K, the best fits of the data to the growth law yield growth exponents of n = 2.2 ± 0.2, 3.0 ± 0.3 and 3.5 ± 0.3 for samples with FeO = 0%, 3% and 10% respectively. Under these conditions the rate
constants, κ, obey an Arrhenius relation with Q = 206 ± 35 kJ/mol and 385 ± 65 kJ/mol for samples with FeO = 3% and 10%. Grain growth of CaTiO3 becomes sluggish when FeO content exceeds 6%. For T ≥ 1523 K, the best fits of the data to the growth law yield n = 2.5 ± 0.2 for both samples with FeO = 3% and 10%. The activation energies (Q ) were determined as 71 ± 30 kJ/mol and 229 ± 45 kJ/mol for samples with FeO = 3% and 10%, respectively. The TEM observations
show a remarkable difference in the distribution and geometry of FeO below and above 1523 K: nanometer-sized particles of
FeO were observed along CaTiO3 grain boundaries in samples annealed at T < 1523 K. No FeO particles were detected along CaTiO3 grain boundaries in samples annealed at T ≥ 1523 K, but large clusters of FeO particles are observed locally indicating a fast separation of FeO from CaTiO3. Thus we conclude that the slow growth rate of CaTiO3 at T < 1523 K is due to the pinning by FeO particles at grain boundary, and that the change of grain growth kinetics in CaTiO3 at T ≥ 1523 K may relate to the separation of FeO from CaTiO3, which we interpret as due to the phase transformation of CaTiO3 at around 1523 K.
Received: 19 June 1998 / Revised, accepted: 24 March 1999 相似文献
8.
Incongruent melting of biotite to spinel in a quartz-free restite at El Joyazo (SE Spain): Textures and reaction characterization 总被引:3,自引:0,他引:3
B. Cesare 《Contributions to Mineralogy and Petrology》2000,139(3):273-284
In the Grt-Bt-Sil restitic xenoliths of El Joyazo (Cerro de Hoyazo), hercynitic spinel is a minor phase commonly associated
with biotite. The possible reaction relationships among biotite and spinel are studied in reaction textures developed around
biotites at their contact with patches of fibrolitic sillimanite and rhyolitic melt. In these textures, resorbed biotite crystals
about 1 mm long are rimmed by a layer of glass <200 μm thick containing spinel and ilmenite; the same glass also fills embayments
in biotite. Spinel forms euhedral crystals <100 μm in size, and ilmenite occurs as smaller anhedral crystals or needles, often
intergrown with spinel. The homogeneous felt-like melt-sillimanite aggregate (“mix”) is richest in glass close to the reaction
rim around biotite. Plagioclase and garnet are located >5 mm away from the reaction texture. Biotite is chemically zoned.
Cores (Bt
1
) have XMg=0.35 ± 0.02 and Ti=0.58 ± 0.01 atoms; whereas the outer rims (Bt
2
) have XMg=0.45 ± 0.01 and Ti up to 0.68 atoms. The hercynite-rich spinel (Spl) has low ZnO content (<0.80 wt%) and XMg=0.26 ± 0.04. The chemical compositions of the mix aggregate represent linear combinations between sillimanite and a silica-rich melt. This melt (melt
1
) is different from that of the layer around biotite (melt
2
), which is also richer in Ca and alkalis. Garnet rims (Grt) have low Ca and Mn, and XMg=0.14. Plagioclase is characterized by large homogeneous cores (Pl
1
, An31 ± 2) and more calcic rims (Pl
2
, An49 ± 6). Matrix analysis in the 9-component (Al-Ca-Fe-K-Mg-Mn-Na-Si-Ti), 9-phase (Bt1-Bt2-Grt-Spl-Ilm-melt2-mix-Pl1-Pl2) system provides the mass balance (in mole units):
This relationship is in excellent agreement with the observed textures and hence is considered a good model for the incongruent
melting of biotite in the xenoliths. The mass-balance indicates that melt production is dominated by the availability of K
from biotite, and that garnet and plagioclase must be involved as reactants, so that the reaction volume is larger than the
melt production site. The melting of biotite, constrained at T=900–950°C and P ≥ 5 kbar, is not a terminal reaction, as its variance in the reduced 8-component multisystem is ≥3.
Received: 1 June 1999 / Accepted: 8 February 2000 相似文献
9.
Near-infrared (NIR) absorption bands related to total water (4000 and 7050 cm−1), OH groups (4500 cm−1) and molecular H2O (5200 cm−1) were studied in two polymerised glasses, a synthetic albitic composition and a natural obsidian. The water contents of the
glasses were determined using Karl Fischer titration. Molar absorption coefficients were calculated for each of the bands
using albitic glasses containing between 0.54 and 9.16 wt.% H2O and rhyolitic glasses containing between 0.97 and 9.20 wt.% H2O. Different combinations of baseline type and intensity measure (peak height/area) for the combination bands at 4500 and
5200 cm−1 were used to investigate the effect of evaluation procedure on calculated hydrous species concentrations. Total water contents
calculated using each of the baseline/molar absorption coefficient combinations agree to within 5.8% relative for rhyolitic
and 6.5% relative for albitic glasses (maximum absolute differences of 0.08 and 0.15 wt.% H2O, respectively). In glasses with water contents >1 wt.%, calculated hydrous species concentrations vary by up to 17% relative
for OH and 11% relative for H2O (maximum absolute differences of 0.33 and 0.43 wt.% H2O, respectively). This variation in calculated species concentrations is typically greater in rhyolitic glasses than albitic.
In situ, micro-FTIR analysis at 300 and 100 K was used to investigate the effect of varying temperature on the NIR spectra of the
glasses. The linear and integral molar absorption coefficients for each of the bands were recalculated from the 100 K spectra,
and were found to vary systematically from the 300 K values. Linear molar absorption coefficients for the 4000 and 7050 cm−1 bands decrease by 16–20% and integral molar absorption coefficients by up to 30%. Depending on glass composition and baseline
type, the integral molar absorption coefficients for the absorption bands related to OH groups and molecular H2O change by up to −5.8 and +7.4%, respectively, while linear molar absorption coefficients show less variation, with a maximum
change of ∼4%. Using the new molar absorption coefficients for the combination bands to calculate species concentrations at
100 K, the maximum change in species concentration is 0.08 wt.% H2O, compared with 0.39 wt.% which would be calculated if constant values were assumed for the combination band molar absorption
coefficients. Almost all the changes in the spectra can therefore be interpreted in terms of changing molar absorption coefficient,
rather than interconversion between hydrous species.
Received: 17 December 1998 / Revised, accepted 8 July 1999 相似文献
10.
Summary
Kristiansenite occurs as a late hydrothermal mineral in vugs in an amazonite pegmatite at Heftetjern, T?rdal, Telemark, Norway.
Tapering crystals, rarely up to 2 mm long, are colourless, white, or slightly yellowish. The mineral has the ideal composition
Ca2ScSn(Si2O7)(Si2O6OH) and is triclinic C1 with cell parameters a = 10.028(1), b = 8.408(1), c = 13.339(2) ?, α = 90.01(1), β = 109.10(1), γ = 90.00(1)°, V = 1062.7(3) ?3 (Z = 4). It has a monoclinic cell within ∼ 0.1 ? and is polysynthetically twinned on {010} by metric merohedry. The strongest
reflections in the X-ray powder pattern are [d in ?, (I
obs), (hkl)]: 5.18 (53) (1–11), 3.146 (100) (004), 3.089 (63) (−222), 2.901 (19) (221), 2.595 (34) (222), 2.142 (17) (−3–31). The Mohs’
hardness is 5?–6; Dcalc. = 3.64 g/cm3; only a mean refractive index of 1.74 could be measured. Scandium enrichment in the Heftetjern pegmatite and the crystal
chemistry of scandium are briefly discussed.
Received April 30, 2001; accepted July 28, 2001 相似文献
11.
Liping Wang Eric J. Essene Youxue Zhang 《Contributions to Mineralogy and Petrology》1999,135(2-3):164-178
Mineral inclusions in pyrope crystals from Garnet Ridge in the Navajo Volcanic Field on the Colorado Plateau are investigated
in this study with emphasis on the oxide minerals. Each pyrope crystal is roughly uniform in composition except for diffusion
halos surrounding some inclusions. The pyrope crystals have near constant Ca:Fe:Mg ratios, 0.3 to 5.7 wt% Cr2O3, and 20 to 220 ppm H2O. Thermobarometric calculations show that pyrope crystals with different Cr contents formed at different depths ranging from
50 km (where T ≈ 600 °C and P = 15 kbar) to 95 km (where T ≈ 800 °C and P = 30 kbar) along the local geotherm. In addition to previously reported inclusions of rutile, spinel and ilmenite, we discovered
crichtonite series minerals (AM21O38, where A = Sr, Ca, Ba and LREE, and M mainly includes Ti, Cr, Fe and Zr), srilankite (ZrTi2O6), and a new oxide mineral, carmichaelite (MO2−x(OH)x, where M = Ti, Cr, Fe, Al and Mg). Relatively large rutile inclusions contain a significant Nb (up to 2.7 wt% Nb2O5), Cr (up to ∼6 wt% Cr2O3), and OH (up to ∼0.9 wt% H2O). The Cr and OH contents of rutile inclusions are positively related to those of pyrope hosts, respectively. Needle- and
blade-like oxide inclusions are commonly preferentially oriented. Composite inclusions consisting mainly of carbonate, amphibole,
phlogopite, chlorapatite, spinel and rutile are interpreted to have crystallized from trapped fluid/melt. These minerals in
composite inclusions commonly occur at the boundaries between garnet host and large silicate inclusions of peridotitic origin,
such as olivine, enstatite and diopside. The Ti-rich oxide minerals may constitute a potential repository for high field strength
elements (HFSE), large ion lithophile elements and light rare earth elements (LREE) in the upper mantle. The composite and
exotic oxide inclusions strongly suggest an episode of metasomatism in the depleted upper mantle beneath the Colorado Plateau,
contemporaneous with the formation of pyrope crystals. Our observations show that mantle metasomatism may deplete HFSE in
metasomatic fluids/melts. Such fluids/melts may subsequently contribute substantial trace elements to island arc basalts,
providing a possible mechanism for HFSE depletion in these rocks.
Received: 20 December 1997 / Accepted: 15 October 1998 相似文献
12.
N. V. Zubkova D. Yu. Pushcharovsky G. Giester E. Tillmanns I. V. Pekov D. A. Kleimenov 《Mineralogy and Petrology》2002,75(1-2):79-88
Summary
The crystal structure of arsentsumebite, ideally, Pb2Cu[(As, S)O4]2(OH), monoclinic, space group P21/m, a = 7.804(8), b = 5.890(6), c = 8.964(8) ?, β = 112.29(6)°, V = 381.2 ?3, Z = 2, dcalc. = 6.481 has been refined to R = 0.053 for 898 unique reflections with I> 2σ(I). Arsentsumebite belongs to the brackebuschite group of lead minerals with the general formula Pb2
Me(XO4)2(Z) where Me = Cu2+, Mn2+, Zn2+, Fe2+, Fe3+; X = S, Cr, V, As, P; Z = OH, H2O. Members of this group include tsumebite, Pb2Cu(SO4)(PO4)(OH), vauquelinite, Pb2Cu(CrO4)(PO4)(OH), brackebuschite, Pb2 (Mn, Fe)(VO4)2(OH), arsenbracke buschite, Pb2(Fe, Zn)(AsO4)2(OH, H2O), fornacite, Pb2Cu(AsO4)(CrO4)(OH), and feinglosite, Pb2(Zn, Fe)[(As, S)O4]2(H2O). Arsentsumebite and all other group members contain M = M–T chains where M = M means edge-sharing between MO6 octahedra and M–T represents corner sharing between octahedra and XO4 tetrahedra. A structural relationship exists to tsumcorite, Pb(Zn, Fe)2(AsO4)2 (OH, H2O)2 and tsumcorite-group minerals Me(1)Me(2)2(XO4)2(OH, H2O)2.
Received June 24, 2000; revised version accepted February 8, 2001 相似文献
13.
The cation distribution of Co, Ni, and Zn between the M1 and M2 sites of a synthetic olivine was determined with a single-crystal
diffraction method. The crystal data are (Co0.377Ni0.396Zn0.227)2SiO4, M
r
= 212.692, orthorhombic, Pbnm, a = 475.64(3), b = 1022.83(8), and c = 596.96(6) pm, V = 0.2904(1) nm3, Z = 4, D
x
= 4.864 g cm−3, and F(0 0 0) = 408.62. Lattice, positional, and thermal parameters were determined with MoKα radiation; R = 0.025 for 1487 symmetry-independent reflections with F > 4σ(F). The site occupancies of Co, Ni, and Zn were determined with synchrotron radiation employing the anomalous dispersion effect
of Co and Ni. The synchrotron radiation data include two sets of intensity data collected at 161.57 and 149.81 pm, which are
about 1 pm longer than Co and Ni absorption edges, respectively. The R value was 0.022 for Co K edge data with 174 independent reflections, and 0.034 for Ni K edge data with 169 reflections. The occupancies are 0.334Co + 0.539Ni + 0.127Zn in the M1 sites, and 0.420Co + 0.253Ni + 0.327Zn
in the M2 sites. The compilation of the cation distributions in olivines shows that the distributions depend on ionic radii
and electronegativities of constituent cations, and that the partition coefficient can be estimated from the equation: ln [(A/B)M1/(A/B)M2] = −0.272 (IR
A
-IR
B
) + 3.65 (EN
A
−EN
B
), where IR (pm) and EN are ionic radius and electronegativity, respectively.
Received: 8 April 1999 / Revised, accepted: 7 September 1999 相似文献
14.
Summary. ?Ca-tourmaline has been synthesized hydrothermally in the presence of Ca(OH)2 and CaCl2-bearing solutions of different concentration at T = 300–700 °C at a constant fluid pressure of 200 MPa in the system CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl. Synthesis of tourmaline was possible at 400 °C, but only above 500 °C considerable amounts of tourmaline formed. Electron
microprobe analysis and X-ray powder data indicate that the synthetic tourmalines are essentially solid solutions between
oxy-uvite, CaMg3- Al6(Si6O18)(BO3)3(OH)3O, and oxy-Mg-foitite, □(MgAl2)Al6(Si6O18)(BO3)3(OH)3O. The amount of Ca ranges from 0.36 to 0.88 Ca pfu and increases with synthesis temperature as well as with bulk Ca-concentration
in the starting mixture. No hydroxy-uvite, CaMg3(MgAl5)(Si6O18)(BO3)3(OH)3(OH), could be synthesized. All tourmalines have < 3 Mg and > 6 Al pfu. The Al/(Al + Mg)-ratio decreases from 0.80 to 0.70
with increasing Ca content. Al is coupled with Mg and Ca via the substitutions Al2□Mg−2Ca−1 and AlMg−1H−1. No single phase tourmaline could be synthesized. Anorthite ( + quartz in most runs) has been found coexisting with tourmaline.
Other phases are chlorite, tremolite, enstatite or cordierite.
Between solid and fluid, Ca is strongly fractionated into tourmaline ( + anorthite). The concentration ratio D = Ca(fluid)/Ca(tur) increases from 0.20 at 500 °C up to 0.31 at 700 °C. For the assemblage turmaline + anorthite + quartz + chlorite or tremolite
or cordierite, the relationship between Ca content in tourmaline and in fluid with temperature can be described by the equation
(whereby T = temperature in °C, Ca(tur) = amount of Ca on the X-site in tourmaline, Ca( fluid) = concentration of Ca2+ in the fluid in mol/l). The investigations may serve as a first guideline to evaluate the possibility to use tourmaline as
an indicator for the fluid composition.
Received July 24, 1998;/revised version accepted October 21, 1999 相似文献
Zusammenfassung. ?Synthese von Ca-Turmelin im System CaO-MgO-Al 2 O 3 -SiO 2 -B 2 O 3 -H 2 O-HCl Im System CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl wurde Ca-Turmalin hydrothermal aus Ca(OH)2 and CaCl2-haltigen L?sungen bei T = 300–700 °C und einem konstanten Fluiddruck von 200 MPa synthetisiert. Die Synthese von Turmalin war m?glich ab 400 °C, aber nur oberhalb von 500 °C bildeten sich deutliche Mengen an Turmalin. Elektronenstrahl-Mikrosondenanalysen und R?ntgenpulveraufnahmen zeigen, da? Mischkristalle der Reihe Oxy-Uvit, CaMg3Al6(Si6O18)(BO3)3(OH)3O, und Oxy-Mg-Foitit, □(MgAl2)Al6(Si6O18)(BO3)3(OH)3O gebildet wurden. Der Anteil an Ca variiert zwischen 0.36 und 0.88 Ca pfu und nimmt mit zunehmender Synthesetemperatur und zunehmender Ca-Konzentration im System zu. Hydroxy-Uvit, CaMg3(MgAl5) (Si6O18)(BO3)3(OH)3(OH), konnte nicht synthetisiert werden. Alle Turmaline haben < 3 Mg und > 6 Al pfu. Dabei nimmt das Al/(Al + Mg)- Verh?ltnis mit zunehmendem Ca-Gehalt von 0.80 auf 0.70 ab. Al ist gekoppelt mit Mg und Ca über die Substitutionen Al2□Mg−2Ca−1 und AlMg−1H−1. Einphasiger Turmalin konnte nicht synthetisiert werden. Anorthit (+ Quarz in den meisten F?llen) koexistiert mit Turmalin. Andere Phasen sind Chlorit, Tremolit, Enstatit oder Cordierit. Ca zeigt eine deutliche Fraktionierung in den Festk?rpern Turmalin (+ Anorthit). Das Konzentrationsverh?ltnis D = Ca(fluid)/Ca(tur) nimmt von 0.20 bei 500 °C auf 0.31 bei 700 °C zu. Für die Paragenese Turmalin + Anorthit + Quarz mit Chlorit oder Tremolit oder Cordierit gilt folgende Beziehung zwischen Ca-Gehalt in Turmalin und Fluid und der Temperatur: (wobei T = Temperatur in °C, Ca(tur) = Anteil an Ca auf der X-Position in Turmalin, Ca(fluid) = Konzentration von Ca2+ im Fluid in mol/l). Die Untersuchungen dienen zur ersten Absch?tzung, ob Turmalin als Fluidindikator petrologisch nutzbar ist.
Received July 24, 1998;/revised version accepted October 21, 1999 相似文献
15.
The spinel solid solution was found to exist in the whole range between Fe3O4 and γ-Fe2SiO4 at over 10 GPa. The resistivity of Fe3−
x
Si
x
O4 (0.0<x<0.288) was measured in the temperature range of 80∼300 K by the AC impedance method. Electron hopping between Fe3+ and Fe2+ in the octahedral site of iron-rich phases gives a large electric conductivity at room temperature. The activation energy
of the electron hopping becomes larger with increasing γ-Fe2SiO4 component. A nonlinear change in electric conductivity is not simply caused by the statistical probability of Fe3+–Fe2+ electron hopping with increasing the total Si content. This is probably because a large number of Si4+ ions occupies the octahedral site and the adjacent Fe2+ keeping the local electric neutrality around Si4+ makes a cluster, which generates a local deformation by Si substitution.
The temperature dependence of the conductivity of solid solutions indicates the Verwey transition temperature, which decreases
from 124(±2) K at x=0 (Fe3O4) to 102(±5) K at x=0.288, and the electric conductivity gap at the transition temperature decreases with Si4+ substitution.
Received: 15 March 2000 / Accepted: 4 September 2000 相似文献
16.
Hydroxyl defects in garnets from mantle xenoliths in kimberlites of the Siberian platform 总被引:12,自引:0,他引:12
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
17.
The 150 m thick late Miocene Graveyard Point sill (GPS) is situated at the Idaho-Oregon border near the southwestern edge
of the western Snake River Plain. It records from bottom to top continuous fractional crystallization of a tholeiitic parent
magma (lower chilled border, FeO/(FeO+MgO) = 0.59, Ni = 90 ppm) towards granophyres (late pods and dikes, FeO/(FeO+MgO) = 0.98,
78 wt% SiO2 3.5 wt% K2O, <4 ppm Ni) showing a typical trend of Fe and P enrichment. Fractionating minerals are olivine (Fo79-Fo2), augite (X
Fe = 0.18−0.95), feldspars (An80Or1-An1Or62), Fe-Ti oxides (Ti-rich magnetite and ilmenite), apatite and in two samples super-calcic pigeonite (Wo18–28 Fs41–54). The granophyres may bear some quartz. Compositionally zoned minerals record a large interval of the fractionation process
in every single sample, but this interval changes with stratigraphic height. In super-calcic pigeonite-bearing samples, olivine
is scarce or lacking and because super-calcic pigeonite occurs as characteristic overgrowths on augite, its formation is interpreted
to be related to the schematic reaction: augite + olivine (component in melt) + SiO2 (in melt) = pigeonite, that defines the cotectic between augite and pigeonite in olivine-saturated basaltic systems. Line
measurements with the electron microprobe reveal that the transition from augite to super-calcic pigeonite is continuous.
However, some crystals show an abrupt “reversal” towards augite after super-calcic pigeonite growth. Two processes compete
with each other in the GPS: fractional crystallization of the bulk liquid (the bulk melt separates from solids and interstitial
liquids in the solidification front) and fractional crystallization of interstitial melt in the solidification front itself.
Interplay between those two processes is proposed to account for the observed variations in mineral chemistry and mineral
textures.
Received: 25 November 1998 / Accepted: 14 June 1999 相似文献
18.
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
19.
H. W. Nesbitt A. G. Schaufuss G. M. Bancroft R. Szargan 《Physics and Chemistry of Minerals》2002,29(1):72-77
Synchrotron excited X-ray photoelectron spectra (SXPS) of hexagonal pyrrhotite reveal three distinct Fe 3d-derived photopeaks within its outer valence band. The t
2gα band (majority spin) is centered at about 2.5 eV, the e
g
α band at about 1.0 eV and the t
2gβ (minority spin) contribution at about 0.25 eV. From these data the ligand field splitting energy is 1.5 (±0.2) eV and the
majority spin pairing energy is 2.25 (±0.2) eV. These are the first such XPS measurements for this mineral. S 3p-derived bonding and non-bonding bands are identified, with the former centred at about 6.5 eV and the latter near 4.5 eV.
The XPS results are remarkably consistent with SCF-Xα scattered wave molecular orbital calculations. Although the calculations
and the collected spectra are consistent, they differ from a recent interpretation of the pyrrhotite valence band. An explanation
for the discrepant results is provided. Auger resonant enhancement of Fe 3d photopeaks at 60 eV photon energy results in the
t
2gα emission (at 2.5 eV) being strongly enhanced and broader than the t
2gβ emission (0.25 eV). The explanation of these observations requires the presence of weak Fe–Fe π and π* crystal (molecular) orbitals located near 2.5 eV, and separated by no more than about 0.5 eV. The π-bonded crystal orbitals
are derived from weak mixing of adjacent Fe t
2g atomic orbitals along the c crystallographic axis.
Received: 15 June 2000 / Accepted: 11 June 2001 相似文献
20.
Summary This study reports foggite and churchite-(Y) from two spatially separate locations in the guano-related phosphate deposit
from the Cioclovina Cave, Romania. Optical microscope observations, powder X-ray diffraction, electron microprobe analyses,
and FTIR were used in the analysis of the two minerals. The chemical composition of foggite was determined to be Ca0.925(Al0.91Fe2+0.016)Σ0.926(P0.991Si0.043)Σ1.034O3.74(OH)2.26 · H2O and churchite-(Y) [(Y0.830Dy0.043Er0.033Gd0.029Yb0.022)Σ0.957Ca0.009]P1.023O4.00 · 2H2O. Chemical analyses of Cioclovina churchite-(Y) clearly revealed enrichment in lanthanides of even atomic number. The refined
unit-cell parameters are for foggite (orthorhombic) a = 9.264(1) ?, b = 21.334(8) ?, c = 5.197(7) ?, and V = 1027.13(8) ?3 (Z = 8); for churchite-(Y) (monoclinic): a = 5.578(8) ?, b = 15.013(6) ?, c = 6.277(8) ?, β = 117.94(4)°, and V = 464.38(5) ?3 (Z = 4). FTIR spectrum of churchite-(Y) exhibits all the bands assigned to the vibrations of PO4, OH, and water groups.
Unlike other documented occurrences of foggite and churchite-(Y), in Cioclovina Cave, the occurrence of these minerals are
related to a process that phosphatized subjacent limestone and various cave sediments (sand, clay, and limy mud) to form a
complex phosphate assemblage. The minerals are presumably derived from phosphate-rich solutions that reacted with clay earth
while moving downward through the sediments. Foggite was formed at the expense of the originally precipitated crandallite.
Locally concentrated yttrium, REE, and dissolved phosphate are probably responsible for the precipitation of churchite-(Y).
Present address: Department of Geology, University of South Florida, Tampa, FL, USA 相似文献