Single crystal hydrostatic compression of (Mg,Mn,Fe,Co)2SiO4 olivines     

Li Zhang 《Physics and Chemistry of Minerals》1998,25(4):308-312

Four synthetic endmember olivines (Mg,Mn, Fe,Co)₂SiO₄ with space group Pbnm were loaded together in one diamond cell mount. Their unit-cell parameters were determined by single crystal X-ray diffraction to 10 GPa. The linear compressibilities β_a, β_b, β_c were 1.53, 2.90, 2.32; 1.45, 3.48, 1.98; 1.35, 3.29, 1.76; and 1.25, 2.82, 2.01×10⁻³ GPa⁻¹ for Mg₂SiO₄, Mn₂SiO₄, Fe₂SiO₄ and Co₂SiO₄, respectively. The b axis is the most compressible direction in all crystals studied. Bulk modulus K_T0 and its first pressure derivative were simultaneously determined for Mg₂SiO₄, Fe₂SiO₄ and Co₂SiO₄ crystals respectively by fitting volume data to a third order Birch-Murnaghan equation of state. They are 127(4) and 4.2(8), 136(3) and 4.1(7), and 144(2) and 4.1(5). The K_T0 and could not simultaneously be determined unambiguously for Mn₂SiO₄. Direct comparisons of unit-cell volumes at high pressure among pairs of olivines reveal anomalous compression behavior of the Mg₂SiO₄ crystal regarding the bulk modulus-volume relationship. This behavior, however, could not be observed in the transition metal olivines (Mn,Fe,Co)₂SiO₄. The distinct electronic configurations of Mg²⁺ and the transition metal cations Mn²⁺, Fe²⁺, and Co²⁺ result in the different compression behaviors of Mg₂SiO₄ and (Mn,Fe,Co)₂SiO₄. Received: 14 April 1997 / Revised, accepted: 29 July 1997  相似文献   

Polarized single-crystal FTIR-spectra of natural staurolite     

Monika Koch-Müller  Klaus Langer  Anton Beran 《Physics and Chemistry of Minerals》1995,22(2):108-114

Polarized infrared absorption spectra of thin single-crystal slabs parallel to (010) and (001) of a staurolite from Pizzo Forno, Ticino, with analyzed composition (Fe_2.9Mg_0.9Zn_0.1Mn_0.1)Al_17.5Ti_0.1(Si_7.7Al_0.3)O₄₈H₃ have been measured in the range of 3000–4000 cm^?1. From the pleochroitic behaviour of the OH-vibrations three groups of bands can be distinguished: the bands of group I, a strong band at 3445 cm^?1 plus a weak shoulder at 3358 cm^?1, and the bands of group II, a weak band centered at 3677 cm^?1 plus a shoulder at 3635 cm^?1, are assigned to the H1 and H2 protons, respectively. The bands of group III, a weak band at 3577 cm^?1 plus a shoulder, cannot be interpreted on the basis of the proton positions known so far. We assign them to an additional proton H3, which is bonded to O1 and shows a bifurcated hydrogen bridge to two O5 in a vacant T2 site.  相似文献   

Geochemical modeling of coal mine drainage, Summit County, Ohio   总被引：4，自引：1，他引：4  

A. Foos 《Environmental Geology》1997,31(3-4):205-210

 Geochemical modeling was used to investigate downstream changes in coal mine drainage at Silver Creek Metro-park, Summit County, Ohio. A simple mixing model identified the components that are undergoing conservative transport (Cl^–, PO₄ ^3–, Ca²⁺, K⁺, Mg²⁺ and Na⁺) and those undergoing reactive transport (DO, HCO₃ ^–, SO₄ ^2–, Fe²⁺, Mn²⁺ and Si). Fe²⁺ is removed by precipitation of amorphous iron-hydroxide. Mn²⁺ are removed along with Fe²⁺ by adsorption onto surfaces of iron-hydroxides. DO increases downstream due to absorption from the atmosphere. The HCO₃ ^– concentration increases downstream as a result of oxidation of organic material. The rate of Fe²⁺ removal from the mine drainage was estimated from the linear relationship between Fe⁺² concentration and downstream distance to be 0.126 mg/s. Results of this study can be used to improve the design of aerobic wetlands used to treat acid mine drainage. Received: 4 June 1996 · Accepted: 17 September 1996  相似文献   

Single-crystal hydrostatic compression of synthetic pyrope, almandine, spessartine, grossular and andradite garnets at high pressures     

Li Zhang  H. Ahsbahs  A. Kutoglu  C. A. Geiger 《Physics and Chemistry of Minerals》1999,27(1):52-58

The compression of synthetic pyrope Mg₃Al₂ (SiO₄)₃, almandine Fe₃Al₂(SiO₄)₃, spessartine Mn₃Al₂ (SiO₄)₃ grossular Ca₃Al₂(SiO₄)₃ and andradite Ca₃Fe₂ (SiO₄)₃ was studied by loading the crystals together in a diamond anvil cell. The unit-cell parameters were determined as a function of pressure by X-ray diffraction up to 15 GPa using neon as a pressure transmitting medium. The unit-cell parameters of pyrope and almandine were measured up to 33 and 21 GPa, respectively, using helium as a pressure medium. The bulk moduli, K _{T 0}, and their first pressure derivatives, K _{T 0} ^′, were simultaneously determined for all five garnets by fitting the volume data to a third order Birch-Murnaghan equation of state. Both parameters can be further constrained through a comparison of volume compressions between pairs of garnets, giving for K _{T 0} and K _{T 0} ^′ 171(2) GPa and 4.4(2) for pyrope, 185(3) GPa and 4.2(3) for almandine, 189(1) GPa and 4.2 for spessartine, 175(1) GPa and 4.4 for grossular and 157(1) GPa and 5.1 for andradite, where the K _{T 0} ^′ are fixed in the case of spessartine, grossular and andradite. Direct comparisons of the unit-cell volumes determined at high pressures between pairs of garnets reveal anomalous compression behavior for Mg²⁺ in the 8-fold coordinated triangular dodecahedron in pyrope. This agrees with previous studies concerning the compression behaviors of Mg²⁺ in 6-fold coordinated polyhedra at high pressures. The results show that simple bulk modulus–volume systematics are not obeyed by garnets. Received: 29 July 1998 / Revised, accepted: 7 April 1999  相似文献   

High pressure single-crystal synthesis, structure and compressibility of the garnet Mn2+ 3Mn3+ 2[SiO4]3     

T. Arlt  T. Armbruster  R. Miletich  P. Ulmer  T. Peters 《Physics and Chemistry of Minerals》1998,26(2):100-106

Single crystals of the garnet Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ and coesite were synthesised from MnO₂-SiO₂ oxide mixtures at 1000°C and 9 GPa in a multianvil press. The crystal structure of the garnet [space group Ia3¯d, a=11.801(2) Å] was refined at room temperature and 100 K from single-crystal X-ray data to R1=2.36% and R1=2.71%, respectively. In contrast to tetragonal Ca₃Mn³⁺ ₂[GeO₄]₃ (space group I4₁/a), the high-pressure garnet is cubic and does not display an ordered Jahn-Teller distortion of octahedral Mn³⁺. A disordered Jahn-Teller distortion either dynamic or static is evidenced by unusual high anisotropic displacement parameters. The room temperature structure is characterised by following bond lengths: Si-O=1.636(4) Å (tetrahedron), Mn³⁺-O=1.995 (4) Å (octahedron), Mn²⁺-O=2.280(5) and 2.409(4) Å (dodecahedron). The cubic structure was preserved upon cooling to 100 K [a=11.788(2) Å] and upon compressing up to 11.8 GPa in a diamond-anvil cell. Pressure variation of the unit cell parameter expressed by a third-order Birch-Murnaghan equation of state led to a bulk modulus K ₀=151.6(8) GPa and its pressure derivatives K′=6.38(19). The peak positions of the Raman spectrum recorded for Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ were assigned based on a calderite Mn²⁺ ₃Fe³⁺ ₂[SiO₄]₃ model extrapolated from andradite and grossular literature data.  相似文献   

Low temperature spectral studies of Mn3+-bearing andalusite and epidote type minerals in the range 30000–5000 cm−1     

Smith  G.  Hålenius  U.  Langer  K. 《Physics and Chemistry of Minerals》1982,8(3):136-142

Polarized absorption spectra of natural piemontite (Ca_1.802Mn ²⁺_0.178 Mg_0.025) (Mn ³⁺_0.829 Fe ³⁺_0.346 Al_1.825) [(Si_2.992Al_0.008) O₁₂OH], viridine (Al_1.945Mn ³⁺_0.033 Fe ³⁺_0.063 Mg_0.003) [O|Si_0.970 O₄], and kanonaite (Al_1.291Mn ³⁺_0.682 Fe ³⁺_0.019 ) [O|Si_1.006 O₄] were measured at 295 and ca. 100 K. For piemontite, lowering the temperature resulted in a sharpening of broad bands in the 10 000–25 000 cm⁻¹ region supporting their assignment to single ion Mn³⁺ in M3 non-centrosymmetric sites.

Alternatively, in kanonaite, temperature behaviour pointed to a slightly stronger influence of vibronic coupling on strong bands near 16 000 and 22 000 cm⁻¹, which supported an interpretation of Mn³⁺ in nearly centrosymmetric M1 sites. Measurements at ca. 100 K show pronounced fine structure in the viridine spectra which is attributed to Fe³⁺. The ɛ values for Mn³⁺ spin-allowed bands in the three minerals lie in the range 18 to 227 [1·g-atom⁻¹·cm⁻¹].

For the same band and polarisation, ɛ values in Mn³⁺-bearing andalusite-type minerals viridine and kanonaite are the same, which indicates an absence of strong magnetic coupling effects between Mn³⁺ ions in the andalusite type structure down to ca. 100 K.

In silicates, the high ɛ values for Mn³⁺ spin-allowed bands, in comparison to those obtained for Fe²⁺ spin-allowed bands from sites of “similar distortion”, is attributed to a higher degree of covalency in the Mn³⁺-O bonds compared to the Fe²⁺-O bonds, as a result of the higher valence state of manganese.

  相似文献   

Topotactic formation of ferrisicklerite from natural triphylite under hydrothermal conditions     

Peter Schmid-Beurmann  Luisa Ottolini  Frédéric Hatert  Thorsten Geisler  Magdalena Huyskens  Volker Kahlenberg 《Mineralogy and Petrology》2013,107(4):501-515

The topotactic oxidation and delithiation reaction from triphylite, Li(Fe,Mn)PO₄, leading to ferrisicklerite, Li_<1(Fe³⁺,Mn²⁺)PO₄, was investigated under hydrothermal conditions. A cuboid cut from a triphylite single-crystal (Palermo Mine, New Hampshire, USA) with the composition Li_0.93(3)(Fe²⁺ _0.733(6),Fe³⁺ _0.015(1),Mn²⁺ _0.210(4),Mg_0.063(2))_1.021(8)P_1.00(2)O₄ in addition with ground bulk material were treated with KMnO₄ and 30 % H₂O₂(aq) as oxidizing agent in a 0.1 N hydrochloric acid solution in the temperature range between 60 and 200 °C. At 120 °C a rim of 0.1 mm thickness of ferrisicklerite had formed around the core of unreacted triphylite. The sharp reaction boundary was clearly visible, due to the reddish brown absorption colors of ferrisicklerite, compared to colorless triphylite. Using single-crystal X-ray diffraction (XRD), secondary ion mass spectrometry (SIMS), electron probe micro-analysis (EPMA) and ⁵⁷Fe-Mössbauer spectroscopy the product ferrisicklerite was characterized and its composition determined as Li_0.30(7)(Fe²⁺ _0.049(1)Fe³⁺ _0.65(2)Mn²⁺ _0.218(5)Mg_0.062(2))_0.98(1)P_1.01(3)O₄, with unit cell parameters a?=?4.795(1), b?=?9.992(4), and c?=?5.886(2) Å. EPMA investigations across the reaction boundary showed no changes in the concentrations of Fe, Mn, Mg, and P. In contrast, SIMS measurements clearly proved the delithiated state of the ferrisicklerite product. Polarization microscopy revealed that the orientation of the ferrisicklerite rim was the same as that of the original triphylite single-crystal, confirming the strictly topotactic character of the reaction.  相似文献   

Dielectric constants of tephroite,fayalite and olivine and the oxide additivity rule     

R. D. Shannon  M. A. Subramanian  S. Hosoya  G. R. Rossman 《Physics and Chemistry of Minerals》1991,18(1):1-6

The dielectric constants and dissipation factors of synthetic tephroite (Mn₂SiO₄), fayalite (Fe₃SiO₄) and a forsteritic olivine (Mg_1.80Fe_0.22SiO₄) were measured at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: tephroite, κ′_a= 8.79 tan δ_a = 0.0006 κ′_b = 10.20 tan δ_b = 0.0006 κ′_c= 8.94 tan δ_c= 0.0008 fayalite, gk′_a = 8.80 tan δ_a = 0.0004 gk′_b= 8.92 tan δ_b = 0.0018 gk′_c = 8.58 tan δ_c = 0.0010 olivine, gk′_a = 7.16 tan δ_a = 0.0006 gk′_b = 7.61 tan δ_b = 0.0008 gk′_c = 7.03 tan δ_c = 0.0006 The low dielectric constant and loss of the fayalite indicate an exceptionally low Fe³⁺ content. An FeO polarizability of 4.18 ų, determined from α_D(FeO) = [α_D (Fe₂SiO₄)-α_D(SiO₂)]/2, is probably a more reliable value for stoichiometric FeO than could be obtained from Fe_xO where x = 0.90–0.95. The agreement between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of oxide polarizabilities according to α_D(M₂M′X₂) = 2α_D(MX) + α_D(M′X₂) is ～+2.8% for tephroite and +0.2% for olivine. The deviation from additivity in tephroite is discussed.  相似文献   

Pressure dependence of electrical conductivity of (Mg,Fe)SiO<Subscript>3</Subscript> ilmenite     

Tomoo Katsura  Sho Yokoshi  Kazuyuki Kawabe  Anton Shatskiy  Maki Okube  Hiroshi Fukui  Eiji Ito  Akifumi Nozawa  Ken-ichi Funakoshi 《Physics and Chemistry of Minerals》2007,34(4):249-255

The electrical conductivity of (Mg_0.93Fe_0.07)SiO₃ ilmenite was measured at temperatures of 500–1,200 K and pressures of 25–35 GPa in a Kawai-type multi-anvil apparatus equipped with sintered diamond anvils. In order to verify the reliability of this study, the electrical conductivity of (Mg_0.93Fe_0.07)SiO₃ perovskite was also measured at temperatures of 500–1,400 K and pressures of 30–35 GPa. The pressure calibration was carried out using in situ X-ray diffraction of MgO as pressure marker. The oxidation conditions of the samples were controlled by the Fe disk. The activation energy at zero pressure and activation volume for ilmenite are 0.82(6) eV and −1.5(2) cm³/mol, respectively. Those for perovskite were 0.5(1) eV and −0.4(4) cm³/mol, respectively, which are in agreement with the experimental results reported previously. It is concluded that ilmenite conductivity has a large pressure dependence in the investigated P–T range.  相似文献   

High-<Emphasis Type="Italic">T</Emphasis> behaviour of gedrite: thermoelasticity,cation ordering and dehydrogenation     

Michele Zema  Mark D. Welch  Roberta Oberti 《Contributions to Mineralogy and Petrology》2012,163(5):923-937

The thermoelastic behaviour of a natural gedrite having the crystal-chemical formula ^ANa_0.47 ^B(Na_0.03 Mg_1.05 Fe_0.86²⁺ Mn_0.02 Ca_0.04) ^C(Mg_3.44 Fe_0.36²⁺ Al_1.15 Ti_0.05⁴⁺) ^T(Si_6.31 Al_1.69)O₂₂ ^W(OH)₂ has been studied by single-crystal X-ray diffraction to 973 K (Stage 1). After data collection at 973 K, the crystal was heated to 1,173 K to induce dehydrogenation, which was registered by significant changes in unit-cell parameters, M1–O3 and M3–O3 bond lengths and refined site-scattering values of M1 and M4 sites. These changes and the crystal-chemical formula calculated from structure refinement show that all Fe²⁺ originally at M4 migrates into the ribbon of octahedrally coordinated sites, where most of it oxidises to Fe³⁺, and there is a corresponding exchange of Mg from the ribbon into M4. The resulting composition is that of an oxo-gedrite with an inferred crystal-chemical formula ^ANa_0.47 ^B(Na_0.03 Mg_1.93 Ca_0.04) ^C(Mg_2.56 Mn_0.02²⁺ Fe_0.10²⁺ Fe_1.22³⁺ Al_1.15 Ti_0.05⁴⁺) ^T(Si_6.31 Al_1.69) O₂₂ ^W[O_1.12²⁻ (OH)_0.88]. This marked redistribution of Mg and Fe is interpreted as being driven by rapid dehydrogenation at the H3A and H3B sites, such that all available Fe in the structure orders at M1 and M3 sites and is oxidised to Fe³⁺. Thermoelastic data are reported for gedrite and oxo-gedrite; the latter was measured during cooling from 1,173 to 298 K (Stage 2) and checked after further heating to 1,273 K (Stage 3). The thermoelastic properties of gedrite and oxo-gedrite are compared with each other and those of anthophyllite.  相似文献   

A computer simulation study of OH defects in Mg2SiO4 and Mg2GeO4 spinels     

M. Blanchard  K. Wright  J. D. Gale 《Physics and Chemistry of Minerals》2005,32(8-9):585-593

Classical atomistic simulation techniques have been used to investigate the energies of hydrogen defects in Mg₂SiO₄ and Mg₂GeO₄ spinels. Ringwoodite (γ-Mg₂SiO₄) is considered to be the most abundant mineral in the lower part of the transition zone and can incorporate large amounts of water in the form of hydroxyls, whereas the germanate spinel (γ-Mg₂GeO₄) corresponds to a low-pressure structural analogue for ringwoodite. The calculated defect energies indicate that the most favourable mechanisms for hydrogen incorporation are coupled either with the reduction of ferric iron or with the creation of tetrahedral vacancies. Hydrogen will go preferentially into tetrahedral vacancies, eventually leading to the formation of the hydrogarnet defect, before associating with other negatively charged point defects. The presence of isolated hydroxyls is not expected. The same trend is observed for germanate, and thus γ-Mg₂GeO₄ could be used as a low-pressure analogue for ringwoodite in studies of water-related defects and their effect on physical properties.  相似文献   

Variation of infrared absorption spectra in the system Bi2Al4−x Fe x O9 (x = 0–4), structurally related to mullite     

D. Voll  A. Beran  H. Schneider 《Physics and Chemistry of Minerals》2006,33(8-9):623-628

The crystal structure of Bi₂Al_4−x Fe _x O₉ compounds (x = 0–4) has striking similarities with the crystal structure of mullite. A complete substitution of Al by Fe³⁺ in both octahedral and tetrahedral sites is a particular structural feature. The infrared (IR) spectra of the Bi₂M₄O₉ compounds (M = Al, Fe³⁺) are characterised by three band groups with band maxima in the 900–800, 800–600 and 600–400 cm⁻¹ region. Based on the spectroscopic results obtained from mullite-type phases, the present study focuses on the composition-dependent analysis of the 900–800 cm⁻¹ band group, which is assigned to Al(Fe³⁺)–O stretching vibrations of the corner-sharing MO₄ tetrahedra. The Bi₂Al₄O₉ and Bi₂Fe₄O₉ endmembers display single bands with maxima centred at 922 and 812 cm⁻¹, respectively. Intermediate Bi₂Al_4−x Fe _x O₉ compounds exhibit a distinct splitting into three relatively sharp bands, which is interpreted in terms of ordering effects within the tetrahedral pairs. Thereby the high-energy component band of the band triplet relates to Al–O–Al conjunctions and the low-energy component band to Fe–O–Fe conjunctions. The intermediate band is assigned to stretching vibrations of Al–O–Fe or Fe–O–Al configurations of the corner-sharing tetrahedral pairs. Bands in the 800–600 cm⁻¹ range are assigned to low-energy stretching vibrations of the MO₄ tetrahedra and to M–O–M bending vibrations of the tetrahedral pairs. Absorptions in the 600–400 cm⁻¹ range are essentially determined by M–O stretching modes of the M cations in octahedral coordination.  相似文献   

Characterization of leached layers on olivine and pyroxenes using high-resolution XPS and density functional calculations     

V.P. Zakaznova-Herzog  H.W. Nesbitt  J.S. Tse 《Geochimica et cosmochimica acta》2008,72(1):69-86

High-resolution core level and valence band (VB) X-ray photoelectron spectra (XPS) of olivine [(Mg_0.87Fe_0.13)₂SiO₄], bronzite [(Mg_0.8Fe_0.2)₂Si₂O₆] and diopside [Ca(Mg_0.8Fe_0.2)Si₂O₆] were collected before and after leaching in pH ∼2 solutions with the Kratos magnetic confinement charge compensation system which minimizes differential charge broadening. The leached samples yield Si 2p, Mg 2p, Ca 2p and O 1s XPS spectral linewidths and lineshapes similar to those collected from the respective pristine samples prior to leaching. As with previous XPS studies on crushed samples, our broadscan XPS spectra show evidence for initial, preferential leaching of cations (i.e., Ca²⁺ and Mg²⁺) from the near-surface of these minerals. The O 1s spectra of leached olivine and pyroxenes show an additional peak due to OH⁻, which arises from H⁺ exchange with near-surface cations (Ca²⁺ and Mg²⁺) via electrophilic attack of H⁺ on the M-O-Si moiety to produce the H₂Mg(M1)SiO_4(surf) complex at olivine surfaces, and two complexes, H₂Mg(M1)Si₂O_6(surf) and H₄Si₂O_6(surf) at diopside and enstatite surfaces. The olivine and pyroxene surface complexes H₂Mg(M1)SiO_4(surf) and H₂Mg(M1)Si₂O_6(surf) have been proposed previously, but the second pyroxene surface complex H₄Si₂O_6(surf) has not. Two electrophilic reactions occur in both olivine and pyroxene. For olivine, the more rapid attacks the M2-O-Si moiety producing H₂Mg(M1)SiO_4(surf); while the second attacks the M1-O-Si moiety ultimately producing H₄SiO₄ which is released to solution. For pyroxenes, the first electrophilic reaction produces H₂Mg(M1)Si₂O_6(surf), while the second produces.H₄Si₂O_6(surf). These two reactions are followed by a nucleophilic attack of H₂O (or H₃O⁺) on Si of H₄Si₂O_6(surf). This reaction is responsible for rupture of the brigding oxygen bond of the Si-O-Si moiety and release of H₄SiO₄ to solution. The intensity of the OH⁻ peak for the leached pyroxenes is about double the OH⁻ intensity for the leached olivine, consistent with the equivalent of about a monolayer of the above surface complexes being formed in all three minerals.Valence band XPS spectra and density functional calculations demonstrate the remarkable insensitivity of the valence band to leaching of Ca²⁺ and Mg²⁺ from the surface layers. This insensitivity is due to a dearth of Ca and Mg valence electron density in the valence band: the Ca-O and Mg-O bonds are highly ionic, with metal-derived s orbital electrons taking on strong O 2p character. The valence band spectrum of leached olivine shows an additional very weak peak at about 13.5 eV, which is assigned to Si 3s valence orbitals in the surface complex H₂Mg(M1)SiO₄, as indicated by high quality density functional calculations on an olivine where Mg²⁺ in M2 is replaced by 2H⁺. The intensity of this new peak is consistent with formation of the equivalent of a monolayer of the surface complex.  相似文献   

Energy transfer among Pb, Ce and Mn in fluorescent calcite from Kuerle, Xinjiang, China     

Aierken Sidike  X.-M. Wang  Alifu Sawuti  H.-J. Zhu  I. Kusachi  N. Yamashita 《Physics and Chemistry of Minerals》2006,33(8-9):559-566

Natural calcite from Kuerle, Xinjiang, China, shows orange-red fluorescence when exposed to short-wave ultraviolet (UV) light (Hg 253.7 nm). Photoluminescence (PL) emission and excitation spectra of the calcite are observed at room temperature in detail. The PL emission spectrum under 208 nm excitation consists of three bands: two UV bands at 325 and 355 nm and an orange-red band at 620 nm. The three bands are ascribed to Pb²⁺, Ce³⁺ and Mn²⁺, respectively, as activators. The Pb²⁺ excitation band is observed at 243 nm, and the Ce³⁺ excitation band at 295 nm. The Pb²⁺ excitation band is also observed by monitoring the Ce³⁺ fluorescence, and the Pb²⁺ and Ce³⁺ excitation bands, in addition to six Mn²⁺ excitation bands, are also observed by monitoring the Mn²⁺ fluorescence. These indicate that four types of the energy transfer can occur in calcite through the following processes: (1) Pb²⁺ → Ce³⁺, (2) Pb²⁺ → Mn²⁺, (3) Ce³⁺ → Mn²⁺ and (4) Pb²⁺ → Ce³⁺ → Mn²⁺.  相似文献   

Synthetic MgGa2O4-Mg2GeO4 spinel solid solution and β-Mg3Ga2GeO8: chemistry, crystal structures, cation ordering, and comparison to Mg2GeO4 olivine     

R. L. Millard  R. C. Peterson  I. P. Swainson 《Physics and Chemistry of Minerals》2000,27(3):179-193

 Structural parameters and cation ordering are determined for four compositions in the synthetic MgGa₂O₄-Mg₂GeO₄ spinel solid solution (0, 8, 15 and 23 mol% Mg₂GeO₄; 1400 °C, 1 bar) and for spinelloid β-Mg₃Ga₂GeO₈ (1350 °C, 1 bar), by Rietveld refinement of room-temperature neutron diffraction data. Sample chemistry is determined by XRF and EPMA. Addition of Mg₂GeO₄ causes the cation distribution of the MgGa₂O₄ component to change from a disordered inverse distribution in end member MgGa₂O₄, ^[4]Ga = x = 0.88(3), through the random distribution, toward a normal cation distribution, x = 0.37(3), at 23 mol% Mg₂GeO₄. An increase in a_o with increasing Mg₂GeO₄ component is correlated with an increase in the amount of Mg on the tetrahedral site, through substitution of 2 Ga³⁺⇄ Mg²⁺+Ge⁴⁺. The spinel exhibits high configurational entropy, reaching 20.2 J mol⁻¹ (four oxygen basis) near the compositional upper limit of the solid solution. This stabilizes the spinel in spite of positive enthalpy of disordering over the solid solution, where ΔH _D  = αx + βx ², α = 22(3), β = −21(3) kJ mol⁻¹. This model for the cation distribution across the join suggests that the empirically determined limit of the spinel solid solution is correlated with the limit of tetrahedral ordering of Mg, after which local charge-balanced substitution is no longer maintained. Spinelloid β-Mg₃Ga₂GeO₈ has cation distribution ^M1[Mg_0.50(2)Ga_0.50(2)] ^M2[Mg_0.96(2)Ga_0.04(2)] ^M3[Mg_0.77(2) Ga_0.23(2)]₂ (Ge_0.5Ga_0.5)₂O₈ (tetrahedral site occupancies are assumed). Octahedral site size is correlated to Mg distribution, where site volume, site distortion, and Mg content follow the relation M1<M3<M2. The disordered cation distribution provides local electrical neutrality in the structure, and stabilization through increased configurational entropy (27.6 J mol⁻¹; eight oxygen basis). Comparison of the crystal structures of Mg_{1+ N} Ga_{2−2 N} Ge _N O₄ spinel, β-Mg₃Ga₂GeO₈, and Mg₂GeO₄ olivine reveals β-Mg₃Ga₂GeO₈ to be a true structural intermediate. Phase transitions across the pseudobinary are necessary to accommodate an increasing divergence of cation size and valence, with addition of Mg₂GeO₄ component. Octahedral volume increases while tetrahedral volume decreases from spinel to β-Mg₃Ga₂GeO₈ to olivine, with addition of Mg and Ge, respectively. Furthermore, M-M distances increase regularly across the join, suggesting that changes in topology reduce cation-cation repulsion. Received: 9 November 1998 / Revised, accepted: 3 August 1999  相似文献   

Crystal field and charge transfer spectrum of (Mg, Fe)SiO3 majorite     

Hans Keppler  Catherine A. McCammon 《Physics and Chemistry of Minerals》1996,23(2):94-98

Majorite of bulk composition Mg_0.86Fe_0.15SiO₃ was synthesized at 19 GPa and 1900 °C at an oxygen fugacity close to the Re/ReO₂ buffer. Optical absorption spectra of polycrystalline samples were measured from 4000 to 25000cm^?1. The following features were observed: (1) Three bands at 4554, 6005 and 8093 cm^?1 due to the ⁵E_g → ⁵T_2g transition of Fe²⁺ in a distorted dodecahedral site. (2) A band at 9340 cm^?1 due to the transition ⁵T_2g → ⁵E_g of octahedral Fe²⁺. (3) A band at 22784 cm^?1 resulting from Fe³⁺, probably in an octahedral site (⁶A_1g → ⁴A_1g, ⁴E_g). (4) A very intense system of Fe²⁺ → Fe³⁺ intervalence charge transfer bands which can be modelled by two Gaussian components centered at 16542 and 20128 cm^?1. The existence of two components in the charge transfer spectrum could be related to the fact that the tetragonal majorite structure may contain Fe³⁺ in two different octahedral sites. The crystal field splitting Δ of Fe²⁺ in dodecahedral coordination is 5717 cm^?1. If a splitting of the ground state in the order of 1000 cm^?1 is assumed, this yields a crystal field stabilization energy (CFSE) of 3930 cm^?1, comparable to the CFSE of Fe²⁺ in pyrope-rich garnet. However, the splitting of ⁵T_2g is significantly higher than in pyrope. This would be consistent with Fe²⁺ preferentially occupying the more distorted one of the two dodecahedral sites in the majorite structure. For octahedral Fe²⁺, Δ= 9340 cm^?1 and CFSE=3736 cm^?1, assuming negligible splitting of the ground state.  相似文献   

Temperature dependence of the polarized electronic absorption spectra of olivines. Part I – fayalite     

K. Ullrich  K. Langer  K. D. Becker 《Physics and Chemistry of Minerals》2002,29(6):409-419

 Polarized electronic absorption spectra of orthorhombic fayalite, Fe₂SiO₄, [E || a(|| Z),E || b(|| X), E || c(|| Y)], space group Pbnm, have been studied in the temperature range 293 ≤T/K ≤ 1273. The spectra were analysed into component bands originating from spin-allowed dd transitions of iron(II) at the different sites, M1 and M2, in the structure. The assignments of bands, made on the basis of the polarization dependence of the spectra and considerations of transition energies, were confirmed by the analysis of the temperature-dependent spectra. The temperature dependencies of integral intensities, half band widths and energy positions of absorptions bands caused by Fe²⁺ on the different octahedral sites, M1 and M2, were evaluated for the individual transitions. Independent of the site symmetry, absorption bands shift to lower energies and half band widths increase on rising temperature. The temperature dependence of band intensities depends on site symmetry. The integral intensities are found to increase with temperature for the transition metal ion on a centrosymmetric site, or remain constant when the site is missing an inversion centre. This is consistent with the general conclusion of Taran et al. (1994). Received: 11 October 2001 / Accepted: 17 January 2002  相似文献   

Water incorporation in synthetic and natural MgAl₂O₄ spinel     

Geoffrey D. Bromiley  Fabrizio Nestola  Ming Zhang 《Geochimica et cosmochimica acta》2010,74(2):705-445

The solubility and incorporation mechanisms of water in synthetic and natural MgAl₂O₄ spinel have been investigated in a series of high-pressure/temperature annealing experiments. In contrast to most other nominally anhydrous minerals, natural spinel appears to be completely anhydrous. On the other hand, non-stoichiometric Al-rich synthetic (defect) spinel can accommodate several hundred ppm water in the form of structurally-incorporated hydrogen. Infrared (IR) spectra of hydrated defect spinel contain one main O-H stretching band at 3343-3352 cm⁻¹ and a doublet consisting of two distinct O-H bands at 3505-3517 cm⁻¹ and 3557-3566 cm⁻¹. IR spectra and structural refinements based on single-crystal X-ray data are consistent with hydrogen incorporation in defect spinel onto both octahedral and tetrahedral O-O edges. Fine structure of O-H bands in IR spectra can be explained by partial coupling of interstitial hydrogen with cation vacancies, or by the effects of Mg-Al disorder on the tetrahedral site. The concentration of cation vacancies in defect spinel is a major control on hydrogen affinity. The commercial availability of large single crystals of defect spinel coupled with high water solubility and similarities in water incorporation mechanisms between hydrous defect spinel and hydrous ringwoodite (Mg₂SiO₄) suggests that synthetic defect spinel may be a useful low-pressure analogue material for investigating the causes and consequences of water incorporation in the lower part of Earth’s mantle transition zone.  相似文献   

Polarized electronic absorption spectra of synthetic (Mg,Fe)-orthopyroxenes,ferrosilite and Fe3+-bearing ferrosilite     

G. Steffen  K. Langer  F. Seifert 《Physics and Chemistry of Minerals》1988,16(2):120-129

The assignment of spin-allowed Fe²⁺-bands in orthopyroxene electronic absorption spectra is revised by studying synthetic bronzite (Mg_0.8 Fe_0.2)₂Si₂O₆, hypersthene (Mg_0.5 Fe_0.5)₂Si₂O₆ and ferrosilite (Fe₂Si₂O₆). Reheating of bronzite and hypersthene single crystals causes a redistribution of the Fe²⁺-ions over the M1 and M2 octahedra, which was determined by Mössbauer spectroscopy and correlated to the intensity change of the spin-allowed Fe²⁺ d-d bands in the polarized absorption spectra. The 11000 cm^-1 band is caused by Fe²⁺ in M1 (⁵B_2g→⁵A_1g) and Fe²⁺ in M2 (⁵A₁→⁵A₁), the 8500 cm^-1 band by Fe²⁺ in M1 (⁵B_2g→⁵B_1g) and the 5000 cm^-1 band by Fe²⁺ in M2 octahedra (⁵A₁→⁵B₁). The Fe²⁺-Fe³⁺ charge transfer band is identified at 12500cm^-1 in the spectra of synthetic Fe³⁺ -Al bearing ferrosilite. This band shows a strong γ-polarization and therefore is caused by Fe²⁺ -Fe³⁺-ions in edge-sharing octahedra.  相似文献   

A study of phase transformation in hedenbergite to 40 GPa at ∼1200° C     

Young-Ho Kim  Li Chung Ming  Murli H. Manghnani 《Physics and Chemistry of Minerals》1989,16(8):757-762

Phase transformations in a natural sample of hedenbergite ((Ca_0.93Fe_0.61Mn_0.34Mg_0.08Na_0.01Zn_0.02Al_0.003)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