Single-crystal X-ray diffraction and spectroscopic studies on humboldtine and lindbergite: weak Jahn–Teller effect of Fe<Superscript>2+</Superscript> ion     

Takuya Echigo  Mitsuyoshi Kimata 《Physics and Chemistry of Minerals》2008,35(8):467-475

The single-crystal of humboldtine [Fe²⁺(C₂O₄) · 2H₂O] was first synthesized and the crystal structure has been refined. Single-crystal X-ray diffraction data were collected using an imaging-plate diffractometer system and graphite-monochromatized MoKα radiation. The crystal structure of humboldtine was refined to an agreement index (R1) of 3.22% calculated for 595 unique observed reflections. The mineral crystallizes in the monoclinic system, space group C2/c, with unit cell dimensions of a = 12.011 (11), b = 5.557 (5), c = 9.920 (9) Å, β = 128.53 (3)?, V = 518.0 (8) Å³, and Z = 4. In this crystal structure, the alternation of oxalate anions [(C₂O₄)^2?] and Fe²⁺ ions forms one-dimensional chain structure parallel to [010]; water molecules (H₂O)⁰ create hydrogen bonds to link the chains, where (H₂O)⁰ is essentially part of the crystal structure. The water molecules with the two lone electron pairs (LEPs) on their oxygen atom are tied obliquely to the chains, because the one lone electron pair is considered to participate in the chemical bonds with Fe²⁺ ions. Humboldtine including hydrogen bonds is isotypic with lindbergite [Mn²⁺(C₂O₄) · 2H₂O]. The donor–acceptor separations of the hydrogen bonds in humboldtine are slightly shorter than those in lindbergite, which suggests that the hydrogen bonds in the former are stronger than those in the latter. The infrared and Raman spectra of single-crystals of humboldtine and lindbergite confirmed the differences in hydrogen-bond geometry. In addition, Fe²⁺–O stretching band of humboldtine was split and broadened in the observed Raman spectrum, owing to the Jahn–Teller effect of Fe²⁺ ion. These interpretations were also discussed in terms of bond-valence theory.  相似文献   

Influence of oxygen fugacity and temperature on the redox state of iron in natural silicic aluminosilicate melts     

M. V. Volovetskii  O. A. Lukanin  V. S. Rusakov  A. A. Kargal’tsev 《Geochemistry International》2012,50(4):330-343

The influence of oxygen fugacity (fO₂) and temperature on the valence and structural state of iron was experimentally studied in glasses quenched from natural aluminosilicate melts of granite and pantellerite compositions exposed to various T-fO₂ conditions (1100–1420°C and 10^?12–10^?0.68 bar) at a total pressure of 1 atm. The quenched glasses were investigated by Mössbauer spectroscopy. It was shown that the effect of oxygen fugacity on the redox state of iron at 1320–1420°C can be described by the equation log(Fe³⁺/Fe²⁺) = k log(fO₂) + q, where k and q are constants depending on melt composition and temperature. The Fe³⁺/Fe²⁺ ratio decreases with decreasing fO₂ (T = const) and increasing temperature (fO₂ = const). The structural state of Fe³⁺ depends on the degree of iron oxidation. With increasing Fe³⁺/Fe²⁺ ≥ 1, the dominant coordination of Fe³⁺ changes from octahedral to tetrahedral. Ferrous iron ions occur in octahedral (and/or five-coordinated) sites independent of Fe³⁺/Fe²⁺.  相似文献   

Synthesis,TEM characterization and thermal behaviour of LiNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxene     

Mario Tribaudino  Geoffrey Bromiley  Haruo Ohashi  Fabrizio Nestola 《Physics and Chemistry of Minerals》2009,36(9):527-536

A pyroxene with composition LiNiSi₂O₆ was synthesized at T = 1,473 K and P = 2.0 GPa; the cell parameters at T = 298 K are a = 9.4169(6) Å, b = 8.4465(7) Å, c = 5.2464(3) Å, β = 110.534(6)°, V = 390.78(3) Å³. TEM examination of the LiNiSi₂O₆ pyroxene showed the presence of h + k odd reflections indicative of a primitive lattice, and of antiphase domains obtained by dark field imaging of the h + k odd reflections. A HT in situ investigation was performed by examining TEM selected area diffraction patterns collected at high temperature and synchrotron radiation powder diffraction. In HTTEM the LiNiSi₂O₆ was examined together with LiCrSi₂O₆ pyroxene. In LiCrSi₂O₆ the h + k odd critical reflections disappear at about 340 K; they are sharp up to the transition temperature and do not change their shape until they disappear. In LiNiSi₂O₆ the h + k odd reflections are present up to sample deterioration at 650 K. A high temperature synchrotron radiation powder diffraction investigation was performed on LiNiSi₂O₆ between 298 and 773 K. The analysis of critical reflections and of changes in cell parameters shows that the space group is P-centred up to the highest temperature. The comparative analysis of the thermal and spontaneous strain contributions in P2₁/c and C2/c pyroxenes indicates that the high temperature strain in P-LiNiSi₂O₆ is very similar to that due to thermal strain only in C2/c spodumene and that a spontaneous strain contribution related to pre-transition features is not apparent in LiNiSi₂O₆. A different high-temperature behaviour in LiNiSi₂O₆ with respect to other pyroxenes is suggested, possibly in relation with the presence of Jahn–Teller distortion of the M1 polyhedron centred by low-spin Ni³⁺.  相似文献   

On the crystal chemistry and elastic behavior of a phlogopite 3<Emphasis Type="Italic">T</Emphasis>     

G. D. Gatta  Marco Merlini  Nicola Rotiroti  Nadia Curetti  Alessandro Pavese 《Physics and Chemistry of Minerals》2011,38(8):655-664

The crystal chemistry and the elastic behavior under isothermal conditions up to 9 GPa of a natural, and extremely rare, 3T-phlogopite from Traversella (Valchiusella, Turin, Western Alps) [(K_0.99Na_0.05Ba_0.01)(Mg_2.60Al_0.20Fe _0.21 ²⁺ )[Si_2.71Al_1.29O₁₀](OH)₂, space group P3₁12, with a = 5.3167(4), c = 30.440(2) Å, and V = 745.16(9) ų] have been investigated by electron microprobe analysis in wavelength dispersion mode, single-crystal X-ray diffraction at 100 K, and in situ high-pressure synchrotron radiation powder diffraction (at room temperature) with a diamond anvil cell. The single-crystal refinement confirms the general structure features expected for trioctahedral micas, with the inter-layer site partially occupied by potassium and sodium, iron almost homogeneously distributed over the three independent octahedral sites, and the average bond distances of the two unique tetrahedra suggesting a disordered Si/Al-distribution (i.e., 〈T1-O〉 ~ 1.658 and 〈T2-O〉 ~ 1.656 Å). The location of the H-site confirms the orientation of the O–H vector nearly perpendicular to (0001). The refinement converged with R ₁(F) = 0.0382, 846 unique reflections with F _O > 4σ(F _O) and 61 refined parameters, and not significant residuals in the final difference-Fourier map of the electron density (+0.77/?0.37 e ^?/ų). The high-pressure experiments showed no phase transition within the pressure range investigated. The P–V data were fitted with a Murnaghan (M-EoS) and a third-order Birch-Murnaghan equation of state (BM-EoS), yielding: (1) M-EoS, V ₀ = 747.0(3) ų, K _T0 = 44.5(24) GPa, and K′ = 8.0(9); (2) BM-EoS, V ₀ = 747.0(3) ų, K _T0 = 42.8(29) GPa, and K′ = 9.9(17). A comparison between the elastic behavior in response to pressure observed in 1M- and 3T-phlogopite is made.  相似文献   

The buffering capacity of lithospheric mantle: implications for diamond formation     

Robert?W.?LuthEmail author  Thomas?Stachel 《Contributions to Mineralogy and Petrology》2014,168(5):1083

Current models for the formation of natural diamond involve either oxidation of a methane-bearing fluid by reaction with oxidized mantle, or reduction of a carbonate-bearing fluid (or melt) by reaction with reduced mantle. Implicit in both models is the ability of the mantle with which the fluid equilibrates to act as an oxidizing or reducing agent, or more simply, to act as a source or sink of O₂. If only redox reactions involving iron are operating, the ability of mantle peridotite to fulfill this role in diamond formation may not be sufficient for either model to be viable. Using the recent experimental recalibration of olivine–orthopyroxene–garnet oxybarometers of Stagno et al. (2013), we re-evaluated the global database of ~200 garnet peridotite samples for which the requisite Fe³⁺/Fe²⁺ data for garnet exist. Relative to the previous calibration of Gudmundsson and Wood (1995), the new calibration yields somewhat more oxidized values of Δlog fO₂ (FMQ), with the divergence increasing from <0.5 units of log fO₂ at ~3 GPa to as much as 1.5 units at 5–6.5 GPa. Globally, there is a range of ~4 log units fO₂ for samples from the diamond stability field at any given pressure. Most samples are sufficiently reduced such that diamond, rather than carbonate, would be stable, and CHO fluids at these conditions would be H₂O-rich (>60 mol%), with CH₄ being the next most abundant species. To ascertain the capacity for mantle peridotite to act as a source or sink of O₂, we developed a new model to calculate the fO₂ for a peridotite at a given P, T, and Fe³⁺/Fe²⁺. The results from this model predict 50 ppm or less O₂ is required to shift a depleted mantle peridotite the observed four log units of fO₂. Coupled with the observed distribution of samples at values of fO₂ intermediate between the most reduced (metal-saturated) and most oxidized (carbonate-saturated) possible values for diamond stability, these results demonstrate that peridotites are very poor sinks or sources of O₂ for possible redox reactions to form diamond. A corollary of the poor redox buffering capacity of cratonic peridotites is that they can be employed as faithful indicators of the redox state of the last metasomatic fluid that passed through them. We propose that diamond formation from CHO fluids is a predictable consequence either of isobaric cooling or of combined cooling and decompression of the fluid as it migrates upward in the lithosphere. This establishes a petrological basis for the observed close connection between subcalcic garnet and diamond: based on high solidus temperatures of harzburgite and dunite effectively precluding dilution of CHO fluids through incipient melts, such highly depleted cratonic peridotites are the preferred locus of diamond formation. Due to a rapid increase in solidus temperature with increasing CH₄ content of the fluid, diamond formation related to reduced CHO fluids may also occur in some cratonic lherzolites.  相似文献   

Cation substitution in synthetic meridianiite (MgSO<Subscript>4</Subscript>·11H<Subscript>2</Subscript>O) I: X-ray powder diffraction analysis of quenched polycrystalline aggregates     

A.?Dominic?FortesEmail author  Frank?Browning  Ian?G.?Wood 《Physics and Chemistry of Minerals》2012,39(5):419-441

Meridianiite, MgSO₄·11H₂O, is the most highly hydrated phase in the binary MgSO₄–H₂O system. Lower hydrates in the MgSO₄–H₂O system have end-member analogues containing alternative divalent metal cations (Ni²⁺, Zn²⁺, Mn²⁺, Cu²⁺, Fe²⁺, and Co²⁺) and exhibit extensive solid solution with MgSO₄ and with one another, but no other undecahydrate is known. We have prepared aqueous MgSO₄ solutions doped with these other cations in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. The solid products have been characterised by X-ray powder diffraction, and the onset of partial melting has been quantified using a thermal probe. We have established that of the seven end-member metal sulfates studied, only MgSO₄ forms an undecahydrate; ZnSO₄ forms an orthorhombic heptahydrate (synthetic goslarite), MnSO₄, FeSO₄, and CoSO₄ form monoclinic heptahydrates (syn. mallardite, melanterite, bieberite, respectively), and CuSO₄ crystallises as the well-known triclinic pentahydrate (syn. chalcanthite). NiSO₄ forms a new hydrate which has been indexed with a triclinic unit cell of dimensions a = 6.1275(1) Å, b = 6.8628(1) Å, c = 12.6318(2) Å, α = 92.904(2)°, β = 97.678(2)°, and γ = 96.618(2)°. The unit-cell volume of this crystal, V = 521.74(1) ų, is consistent with it being an octahydrate, NiSO₄·8H₂O. Further analysis of doped specimens has shown that synthetic meridianiite is able to accommodate significant quantities of foreign cations in its structure; of the order 50 mol. % Co²⁺ or Mn²⁺, 20–30 mol. % Ni²⁺ or Zn²⁺, but less than 10 mol. % of Cu²⁺ or Fe²⁺. In three of the systems we examined, an ‘intermediate’ phase occurred that differed in hydration state both from the Mg-bearing meridianiite end-member and the pure dopant end-member hydrate. In the case of CuSO₄, we observed a melanterite-structured heptahydrate at Cu/(Cu + Mg) = 0.5, which we identify as synthetic alpersite [(Mg_0.5Cu_0.5)SO₄·7H₂O)]. In the NiSO₄- and ZnSO₄-doped systems we characterised an entirely new hydrate which could also be identified to a lesser degree in the CuSO₄- and the FeSO₄-doped systems. The Ni-doped substance has been indexed with a monoclinic unit-cell of dimensions a = 6.7488(2) Å, b = 11.9613(4) Å, c = 14.6321(5) Å, and β = 95.047(3)°, systematic absences being indicative of space-group P2₁/c with Z = 4. The unit-cell volume, V = 1,176.59(5) ų, is consistent with it being an enneahydrate [i.e. (Mg_0.5Ni_0.5)SO₄·9H₂O)]. Similarly, the new Zn-bearing enneahydrate has refined unit cell dimensions of a = 6.7555(3) Å, b = 11.9834(5) Å, c = 14.6666(8) Å, β = 95.020(4)°, V = 1,182.77(7) ų, and the new Fe-bearing enneahydrate has refined unit cell dimensions of a = 6.7726(3) Å, b = 12.0077(3) Å, c = 14.6920(5) Å, β = 95.037(3)°, and V = 1,190.20(6) ų. The observation that synthetic meridianiite can form in the presence of, and accommodate significant quantities of other ions increases the likelihood that this mineral will occur naturally on Mars—and elsewhere in the outer solar system—in metalliferous brines.  相似文献   

Droninoite,Ni<Subscript>3</Subscript>Fe<Superscript>3+</Superscript>Cl(OH)<Subscript>8</Subscript> · 2H<Subscript>2</Subscript>O,a new hydrotalcite-group mineral species from the weathered Dronino meteorite     

N. V. Chukanov  I. V. Pekov  L. A. Levitskaya  A. E. Zadov 《Geology of Ore Deposits》2009,51(8):767-773

A new mineral, droninoite, was found in a fragment of a weathered Dronino iron meteorite (which fell near the village of Dronino, Kasimov district, Ryazan oblast, Russia) as dark green to brown fine-grained (the size of single grains is not larger than 1 μm) segregations up to 0.15 × 1 × 1 mm in size associated with taenite, violarite, troilite, chromite, goethite, lepidocrocite, nickelbischofite, and amorphous Fe³⁺ hydroxides. The mineral was named after its type locality. Aggregates of droninoite are earthy and soft; the Mohs hardness is 1–1.5. The calculated density is 2.857 g/cm³. Under a microscope, droninoite is dark gray-green and nonpleochroic. The mean (cooperative for fine-grained aggregate) refractive index is 1.72(1). The IR spectrum indicates the absence of S O ₄ ^2? and C O ₃ ^2? anions. Chemical composition (electron microprobe, partition of total iron into Fe²⁺ and Fe³⁺ made on the basis of the ratio (Ni + Fe²⁺): Fe³⁺ = 3: 1; water is calculated from the difference) is as follows, wt %: 36.45 NiO, 12.15 FeO, 17.55 Fe₂O₃, 23.78 H₂O, 13.01 Cl, ?O=Cl₂ ?2.94, total is 100.00. The empirical formula (Z = 6) is Ni_2.16Fe _0.75 ²⁺ Fe _0.97 ³⁺ Cl_1.62(OH)_7.10 · 2.28H₂O. The simplified formula is Ni₃Fe³⁺Cl(OH)₈ · 2H₂O. Droninoite is trigonal, space group R \(\bar 3\) m, R3m, or R32; a = 6.206(2), c = 46.184(18) Å; V = 1540.4(8) ų. The strong reflections in the X-ray powder diffraction pattern [d, Å (I, %) (hkl)] are 7.76(100)(006), 3.88(40)(0.0.12), 2.64(25)(202, 024), 2.32(20)(0.2.10), 1.965(0.2.16). The holotype specimen is deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, registration number 3676/1.  相似文献   

Effect of Fenton process on treatment of simulated textile wastewater: optimization using response surface methodology     

S. Sharma  S. Kapoor  R. A. Christian 《International Journal of Environmental Science and Technology》2017,14(8):1665-1678

A large portion of water is consumed during various textile operations thereby discharging wastewaters with pollutants of huge environmental concern. The treatment of such wastewaters has promising impact in the field of environmental engineering. In this work, Fenton oxidation treatment was engaged to treat simulated textile wastewater. Box–Behnken design and response surface methodology were employed to optimize the efficiency of Fenton process. Iron dose, peroxide dose and pH were considered as input variables while the responses were taken as chemical oxygen demand and color removal. A total of 17 experiments were conducted and analyzed using second-order quadratic model. The quadratic models generated for chemical oxygen demand and color removal efficiencies were validated using analysis of variances, and it was found that the experimental data fitted the second-order model quite effectively. Analysis of variances demonstrated high values of coefficient of determination (R ²) for chemical oxygen demand and color removal efficiencies with values of 0.9904 and 0.9963 showing high conformation of predicted values to the experimental ones. Perturbation plots suggested that the iron dosage produced the maximum effect on both chemical oxygen demand and color removal efficiencies. The optimum parameters were determined as Fe²⁺ dose—550 mg/L, H₂O₂ dose—5538 mg/L, pH—3.3 with corresponding chemical oxygen demand and color removal efficiencies of 73.86 and 81.35%. Fenton process was found efficient in treatment of simulated textile wastewater, and optimization using response surface methodology was found satisfactory as well as relevant. From the present study, it can also be concluded that if this method is used as pretreatment integrated with biological treatment, it can lead to eco-friendly solution for treatment of textile wastewaters.  相似文献   

The relevance of bisphenol A adsorption during Fenton’s oxidation     

A. Žgajnar Gotvajn  M. Bistan  T. Tišler  A. J. Englande  J. Zagorc-Končan 《International Journal of Environmental Science and Technology》2013,10(6):1141-1148

The aim of this research was to assess the efficiency of Fenton’s oxidation for degradation of endocrine disruptor bisphenol A (BPA) with emphasis on extent of accompanying adsorption. Adsorption on the waste sludge resulting from the Fenton’s oxidation could represent a significant impact on the final removal efficiency of BPA. Fenton’s oxidation was accomplished at two concentrations of BPA (0.228 and 22.8 mg L^?1); both at the selected molar ratio of reagents Fe²⁺:H₂O₂ (1:10), as a function of reaction time. The kinetics of adsorption of BPA on waste sludge was determined for the same two concentrations of BPA at two concentrations of waste sludge (0.1 and 6.0 g L^?1). In addition to changing concentrations of BPA and sludge, the adsorption process was also influenced by parameters such as temperature, pH and contact time. Adsorption isotherms were determined. Oxidation and adsorption were monitored by gas chromatography combined with mass spectrum. It has been confirmed that BPA is not completely oxidized in Fenton’s oxidation, because it is adsorbed to formed waste ferric sludge and thus necessary precautions for sludge deposition must be observed.  相似文献   

Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste     

G. Diego Gatta  Nicola Rotiroti  Martin Fisch  Milen Kadiyski  Thomas Armbruster 《Physics and Chemistry of Minerals》2008,35(9):521-533

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.  相似文献   

Removal of acetaminophen from hospital wastewater using electro-Fenton process     

Saeid Ahmadzadeh  Maryam Dolatabadi 《Environmental Earth Sciences》2018,77(2):53

The current work deals with efficient removal of acetaminophen (AC) from hospital wastewater using electro-Fenton (EF) process. The degradation yield of 99.5% was obtained under optimal experimental conditions, namely 5.75 mg L^?1 initial AC concentration, 2.75 pH solution, 3-cm inter-electrode distance, 100 mg L^?1 KCl electrolyte, 122.5 µL L^?1 H₂O₂, 8 mA cm^?2 current density at equilibrium time of 8 min. Analysis of variance (ANOVA) suggested that the effect of mentioned operating parameters was statistically significant on the AC removal. The low probability amount of P value (P < 0.0001), the Fisher’s F-value of 65.91, and correlation coefficient of the model (R² = 0.9545) revealed a satisfactory correlation between the experimental and the predicted values of AC removal. The predicted removal efficiency of 99.4% was in satisfactory agreement with the obtained experimental removal efficiency of 98.7%. The AC degradation during the EF followed a first-order kinetic model with rate constants (K_app) of 0.6718 min^?1. Using the ordinary radical scavengers revealed that main mechanism of AC degradation controlled by the hydroxyl free radicals produced throughout the EF process. The excess amount of iron (II) scavenged the active radicals and diminished the concentration of ^·OH available to react with AC. The optimum molar ratio of H₂O₂ to Fe²⁺ was found to be 2.5. The developed EF process as a promising technique applied for treatment of real samples.  相似文献   

High-pressure behavior of natural single-crystal epidote and clinozoisite up to 40 GPa   总被引：2，自引：0，他引：2  

Fei Qin  Xiang Wu  Ying Wang  Dawei Fan  Shan Qin  Ke Yang  Joshua P. Townsend  Steven D. Jacobsen 《Physics and Chemistry of Minerals》2016,43(9):649-659

The comparative compressibility and high-pressure stability of a natural epidote (0.79 Fe-total per formula unit, Fe_tot pfu) and clinozoisite (0.40 Fe_tot pfu) were investigated by single-crystal X-ray diffraction and Raman spectroscopy. The lattice parameters of both phases exhibit continuous compression behavior up to 30 GPa without evidence of phase transformation. Pressure–volume data for both phases were fitted to a third-order Birch–Murnaghan equation of state with V ₀ = 461.1(1) ų, K ₀ = 115(2) GPa, and \(K_{0}^{'}\) = 3.7(2) for epidote and V ₀ = 457.8(1) ų, K ₀ = 142(3) GPa, and \(K_{0}^{'}\) = 5.2(4) for clinozoisite. In both epidote and clinozoisite, the b-axis is the stiffest direction, and the ratios of axial compressibility are 1.19:1.00:1.15 for epidote and 1.82:1.00:1.19 for clinozoisite. Whereas the compressibility of the a-axis is nearly the same for both phases, the b- and c-axes of the epidote are about 1.5 times more compressible than in clinozoisite, consistent with epidote having a lower bulk modulus. Raman spectra collected up to 40.4 GPa also show no indication of phase transformation and were used to obtain mode Grüneisen parameters (γ _i) for Si–O vibrations, which were found to be 0.5–0.8, typical for hydrous silicate minerals. The average pressure coefficient of Raman frequency shifts for M–O modes in epidote, 2.61(6) cm^?1/GPa, is larger than found for clinozoisite, 2.40(6) cm^?1/GPa, mainly due to the different compressibility of FeO₆ and AlO₆ octahedra in M3 sites. Epidote and clinozoisite contain about 2 wt% H₂O are thus potentially important carriers of water in subducted slabs.  相似文献   

Geochemistry and origin of Dehoo manganese deposit,south Zahedan,southeastern Iran     

Mohammad Lotfi  Mahmoudreza Kahrazehi  Majid Ghaderi 《Arabian Journal of Geosciences》2017,10(6):142

Dehoo manganese deposit is located 52 km to the south of Zahedan in Sistan and Baluchestan Province, southeastern Iran. This deposit that lies in the central part of the Iranian Flysch Zone is lenticular in shape and lies above the micritic limestone-radiolarite cherts of the upper Cretaceous ophiolite unit. It is hosted within the reddish to brown radiolarite cherts and in places interlinks with them, so that the radiolarite chert packages play a key role for Mn mineralization in the region. Investigated ore-paragenetic successions and the geochemical characteristics of the Dehoo deposit were studied by means of major oxide, trace, and rare earth element (REE) contents that provide information as to the mineral origin. Strong positive correlations were found between major oxides and trace elements (Al₂O₃-TiO₂, r = 0.95; TiO₂-MgO, r = 0.94; Fe₂O₃-Al₂O₃, r = 0.90; MgO-Al₂O₃, r = 0.84; MgO-Fe₂O₃, r = 0.88; Fe₂O₃-TiO₂, r = 0.91; Fe₂O₃-K₂O, r = 0.74; Al₂O₃-K₂O, r = 0.69; Al₂O₃-V, r = 0.72; TiO₂-V, r = 0.73, and MgO-V, r = 0.69) that testify to the contribution of mafic terrigenous detrital material to the deposit. Chondrite-normalized REE patterns of all ore samples are characterized by negative Ce (0.06–0.15, average 0.10) and slightly positive Eu (0.29–0.45, average 0.36) anomalies. Based on ratios of Mn/Fe (average 56.23), Co/Ni (average 0.33), Co/Zn (average 0.38), U/Th (average 3.40), La/Ce (average 1.45), La_n/Nd_n (average 2.16), Dy_n/Yb_n (average 0.33), and light REE/heavy REE (average 8.40; LREE > HREE), as well as Ba (average 920 ppm) and total REE contents (average 6.96 ppm) negative Ce and positive Eu anomalies, Dehoo could be considered a predominantly submarine hydrothermal Mn deposit complemented by terrigenous detrital mafic material.  相似文献   

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods   总被引：1，自引：0，他引：1  

M. Koch-Müller  I. Abs-Wurmbach  D. Rhede  V. Kahlenberg  S. Matsyuk 《Physics and Chemistry of Minerals》2007,34(9):663-678

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.  相似文献   

Crystal structure and refined formula of garyansellite Mg<Subscript>2</Subscript>Fe<Superscript>3+</Superscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH) · 2H<Subscript>2</Subscript>O     

N. V. Zubkova  I. V. Pekov  A. V. Kasatkin  N. V. Chukanov  D. A. Ksenofontov  D. Yu. Pushcharovsky 《Doklady Earth Sciences》2016,467(1):299-302

Single-crystal study of the structure (R = 0.0268) was performed for garyansellite from Rapid Creek, Yukon, Canada. The mineral is orthorhombic, Pbna, a = 9.44738(18), b = 9.85976(19), c = 8.14154(18) Å, V = 758.38(3) ų, Z = 4. An idealized formula of garyansellite is Mg₂Fe³⁺(PO₄)₂(OH) · 2H₂O. Structurally the mineral is close to other members of the phosphoferrite–reddingite group. The structure contains layers of chains of M(2)O₄(OH)(H₂O) octahedra which share edges to form dimers and connected by common edges with isolated from each other M(1)O₄(H₂O)₂ octahedra. The neighboring chains are connected to the layer through the common vertices of M(2) octahedra and octaahedral layers are linked through PO₄ tetrahedra.  相似文献   

Behavior of 10-Å phase at low temperatures     

P. F. Zanazzi  P. Comodi  S. Nazzareni  N. Rotiroti  S. van Smaalen 《Physics and Chemistry of Minerals》2007,34(1):23-29

The thermal evolution of 10-Å phase Mg₃Si₄O₁₀(OH)₂·H₂O, a phyllosilicate which may have an important role in the storage/release of water in subducting slabs, was studied by X-ray single-crystal diffraction in the temperature range 116–293 K. The lattice parameters were measured at several intervals both on cooling and heating. The structural model was refined with intensity data collected at 116 K and compared to the model refined at room temperature. As expected for a layer silicate on cooling in this temperature range, the a and b lattice parameters undergo a small linear decrease, α _a  = 1.7(4) 10^?6 K^?1 and α _b  = 1.9(4) 10^?6 K^?1, where α is the linear thermal expansion coefficient. The greater variation is along the c axis and can be modeled with the second order polynomial c _T  = c ₂₉₃(1 + 6.7(4)10^?5 K^?1ΔT + 9.5(2.5)10^?8 K^?2(ΔT)²) where ΔT = T ? 293 K; the monoclinic angle β slightly increased. The cell volume thermal expansion can be modeled with the polynomial V _T  = V ₂₉₃ (1 + 8.0 10^?5 K^?1 ΔT + 1.4 10^?7 K^?2 (ΔT)²) where ΔT = T ? 293 is in K and V in ų. These variations were similar to those expected for a pressure increase, indicating that T and P effects are approximately inverse. The least-squares refinement with intensity data measured at 116 K shows that the volume of the SiO₄ tetrahedra does not change significantly, whereas the volume of the Mg octahedra slightly decreases. To adjust for the increased misfit between the tetrahedral and octahedral sheets, the tetrahedral rotation angle α changes from 0.58° to 1.38°, increasing the ditrigonalization of the silicate sheet. This deformation has implications on the H-bonds between the water molecule and the basal oxygen atoms. Furthermore, the highly anisotropic thermal ellipsoid of the H₂O oxygen indicates positional disorder, similar to the disorder observed at room temperature. The low-temperature results support the hypothesis that the disorder is static. It can be modeled with a splitting of the interlayer oxygen site with a statistical distribution of the H₂O molecules into two positions, 0.6 Å apart. The resulting shortest O_bas–O_W distances are 2.97 Å, with a significant shortening with respect to the value at room temperature. The low-temperature behavior of the H-bond system is consistent with that hypothesized at high pressure on the basis of the Raman spectra evolution with P.  相似文献   

Chromium solubility in anhydrous Phase B     

Luca Bindi  Ekaterina A. Sirotkina  Andrey V. Bobrov  Fabrizio Nestola  Tetsuo Irifune 《Physics and Chemistry of Minerals》2016,43(2):103-110

The crystal structure and chemical composition of a crystal of (Mg_14?x Cr _x )(Si_5?x Cr _x )O₂₄ (x ≈ 0.30) anhydrous Phase B (Anh-B) synthesized in the model system MgCr₂O₄–Mg₂SiO₄ at 12 GPa and 1600 °C have been investigated. The compound was found to be orthorhombic, space group Pmcb, with lattice parameters a = 5.900(1), b = 14.218(2), c = 10.029(2) Å, V = 841.3(2) Å³ and Z = 2. The structure was refined to R ₁ = 0.065 using 1492 independent reflections. Chromium was found to substitute for both Mg at the M3 site (with a mean bond distance of 2.145 Å) and Si at the octahedral Si1 site (mean bond distance: 1.856 Å), according to the reaction Mg²⁺ + Si⁴⁺ = 2Cr³⁺. Such substitutions cause a reduction in the volume of the M3 site and an increase in the volume of the Si-dominant octahedron with respect to the values typically observed for pure Anh-B and Fe²⁺-bearing Anh-B. Taking into account that Cr³⁺ is not expected to be Jahn–Teller active, it appears that both the Cr³⁺–for–Mg and Cr³⁺–for–Si substitutions in the Anh-B structure decrease the distortion of the octahedra. Electron microprobe analysis gave the Mg_13.66(8)Si_4.70(6)Cr_0.62(4)O₂₄ stoichiometry for the studied phase. The successful synthesis of this phase provides new information for the possible mineral assemblages occurring in the Earth’s deep upper mantle and shed new light on the so-called X discontinuity that has been observed at 275–345 km depth in several subcontinental and subduction zone environments.  相似文献   

Single-crystal X-ray diffraction study of synthetic sodium–hydronium jarosite     

Jens Najorka  James M. T. Lewis  John Spratt  Mark A. Sephton 《Physics and Chemistry of Minerals》2016,43(5):377-386

Na–H₃O jarosite was synthesized hydrothermally at 413 K for 8 days and investigated using single-crystal X-ray diffraction (XRD) and electron microprobe analysis (EMPA). The chemical composition of the studied crystal is [Na_0.57(3) (H₃O)_0.36 (H₂O)_0.07]^A Fe_2.93(3) (SO₄)₂ (OH)_5.70 (H₂O)_0.30, and Fe deficiency was confirmed by both EMPA and XRD analysis. The single-crystal XRD data were collected at 298 and 102 K, and crystal structures were refined in space group \( R\overline{3}m\). The room-temperature data match structural trends of the jarosite group, which vary linearly with the c axis. The low-temperature structure at 102 K shows an anisotropic decrease in the unit cell parameters, with c and a decreasing by 0.45 and 0.03 %, respectively. Structural changes are mainly confined to the A site environment. Only minor changes occur in FeO₆ and SO₄ polyhedra. The structure responds upon cooling by increasing bond length distortion and by decreasing quadratic elongation of the large AO₁₂ polyhedra. The structural parameters at low temperature follow very similar patterns to structural changes that correspond to compositional variation in the jarosite group, which is characterised by the flexibility of AO₁₂ polyhedra and rigidity of Fe(OH)₄O₂–SO₄ layers. The most flexible areas in the jarosite structure are localized at AO₁₂ edges that are not shared with neighbouring FeO₆ octahedra. Importantly, for the application of XRD in planetary settings, the temperature-related changes in jarosite can mimic compositional change.  相似文献   

Structural evolution of hemimorphite at high pressure up to 4.2 GPa     

Yurii V. Seryotkin  Vladimir V. Bakakin 《Physics and Chemistry of Minerals》2011,38(9):679-684

The high-pressure structural evolution of hemimorphite, Zn₄Si₂O₇(OH)₂·H₂O, a = 8.3881(13), b = 10.7179(11), c = 5.1311(9) Å, V = 461.30(12) Å³, space group Imm2, Z = 2, was studied by single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions up to 4.2 GPa. In the pressure range of 0.0001–2.44 GPa, the unit-cell parameters change almost linearly. The phase transition (probably of the second order) with symmetry reduction from Imm2 (hemimorphite-I) to Pnn2 (hemimorphite-II) was found near 2.5 GPa. The structure compressibility increases somewhat above the phase transition. Namely, the initial unit-cell volume decreases by 3.6% at 2.44 GPa and by 7.2% at 4.20 GPa. The hemimorphite framework can be described as built up of secondary building units (SBU) Zn₄Si₂O₇(OH)₂. These blocks are combined to form the rods arranged along the c-axis; these rods are multiplied by basic and I-translations of orthorhombic unit cell. The symmetry reduction is caused by the rotation of the rods along their axis. In hemimorphite-I, the compression affects mainly the SBU dimensions, whereas a rectangular section of the channels having mm2 symmetry remains practically unchanged. An appreciable decrease in this section in hemimorphite-II is determined by its oblique distortion with the loss of m planes. It results from opposite rotation of adjacent SBU, which also leads into the loss of I-translation. In hemimorphite-I, the coordination of H₂O molecules is fourfold planar; the hydrogen-bonded hydroxyls and H₂O molecules form infinite ribbons along the c-axis. In hemimorphite-II, an additional short H₂O–O contact appears as a result of asymmetric deformation of the channels. The appearance of this new contact provides the possibility for re-orientation of hydrogen bonds. The planar coordination of H₂O molecules changes to tetrahedral and the ribbons are transformed to islands (OH)₂–H₂O.  相似文献   

Elastic behavior of vanadinite,Pb<Subscript>10</Subscript>(VO<Subscript>4</Subscript>)<Subscript>6</Subscript>Cl<Subscript>2</Subscript>, a microporous non-zeolitic mineral     

G. Diego Gatta  Yongjae Lee  Chi-Chang Kao 《Physics and Chemistry of Minerals》2009,36(6):311-317

The high-pressure behavior of a vanadinite (Pb₁₀(VO₄)₆Cl₂, a = b = 10.3254(5), c = 7.3450(4) Å, space group P6₃/m), a natural microporous mineral, has been investigated using in-situ HP-synchrotron X-ray powder diffraction up to 7.67 GPa with a diamond anvil cell under hydrostatic conditions. No phase transition has been observed within the pressure range investigated. Axial and volume isothermal Equations of State (EoS) of vanadinite were determined. Fitting the P–V data with a third-order Birch-Murnaghan (BM) EoS, using the data weighted by the uncertainties in P and V, we obtained: V ₀ = 681(1) Å³, K ₀ = 41(5) GPa, and K′ = 12.5(2.5). The evolution of the lattice constants with P shows a strong anisotropic compression pattern. The axial bulk moduli were calculated with a third-order “linearized” BM-EoS. The EoS parameters are: a ₀ = 10.3302(2) Å, K ₀(a) = 35(2) GPa and K′(a) = 10(1) for the a-axis; c ₀ = 7.3520(3) Å, K ₀(c) = 98(4) GPa, and K′(c) = 9(2) for the c-axis (K ₀(a):K ₀(c) = 1:2.80). Axial and volume Eulerian-finite strain (fe) at different normalized stress (Fe) were calculated. The weighted linear regression through the data points yields the following intercept values: Fe _a (0) = 35(2) GPa for the a-axis, Fe _c (0) = 98(4) GPa for the c-axis and Fe _V (0) = 45(2) GPa for the unit-cell volume. The slope of the regression lines gives rise to K′ values of 10(1) for the a-axis, 9(2) for the c-axis and 11(1) for the unit cell-volume. A comparison between the HP-elastic response of vanadinite and the iso-structural apatite is carried out. The possible reasons of the elastic anisotropy are discussed.  相似文献