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1.
The crystal structure of four birefringent andradite samples (two from Arizona, one from Madagascar, and one from Iran) was refined with the Rietveld method, space group $Ia\overline{3} d$ , and monochromatic synchrotron high-resolution powder X-ray diffraction (HRPXRD) data. Each sample contains an assemblage of three different cubic phases. From the electron-microprobe (EMPA) results, fine-scale intergrowths in the Arizona-2 and Madagascar samples appear homogeneous with nearly identical compositions of {Ca2.99Mg0.01}Σ3[ ${\text{Fe}}_{1.99}^{3 + }$ ${\text{Mn}}_{0.01}^{3 + }$ ]Σ2(Si2.95Al0.03 ${\text{Fe}}_{0.02}^{3 + }$ )Σ3O12, Adr98 (Arizona-2), and Adr97 (Madagascar). Both samples are near-end-member andradite, ideally {Ca3}[ ${\text{Fe}}_{2}^{3 + }$ ](Si3)O12, so cation ordering in the X, Y, or Z sites is not possible. Because of the large-scale intergrowths, the Arizona-1 and Iran samples contain three different compositions. Arizona-1 has compositions Adr97 (phase-1), Adr93Grs4 (phase-2), and Adr87Grs11 (phase-3). Iran sample has compositions Adr86Uv12 (phase-1), Adr69Uv30 (phase-2), and Adr76Uv22 (phase-3). The crystal structure of the three phases within each sample was modeled quite well as indicated by the Rietveld refinement statistics of reduced χ2 and overall R (F 2) values of, respectively, 1.980 and 0.0291 (Arizona-1); 1.091 and 0.0305 (Arizona-2); 1.362 and 0.0231 (Madagascar); and 1.681 and 0.0304 (Iran). The dominant phase for each sample has the following unit-cell parameters (Å) and weight fractions (%): a = 12.06314(1), 51.93(9) (Arizona-1); 12.04889(1), 52.47(1) (Arizona-2); 12.06276(1), 52.21(8) (Madagascar); and 12.05962(2), 63.3(1) (Iran). For these dominant phases, the distances and site occupancy factors (sofs) in terms of neutral atoms at the Ca(X), Fe(Y), and Si(Z) sites are as follows: <Ca–O> = 2.4348, Fe–O = 2.0121(6), Si–O = 1.6508(6) Å; Ca(sof) = 0.955(2), Fe(sof) = 0.930(2), and Si(sof) = 0.917(2) (Arizona-1); <Ca–O> = 2.4288, Fe–O = 2.0148(7), Si–O = 1.6476(7) Å; Ca(sof) = 0.953(2), Fe(sof) = 0.891(2), and Si(sof) = 0.927(2) (Arizona-2); <Ca–O> = 2.4319, Fe–O = 2.0220(6), Si–O = 1.6460(6) Å; Ca(sof) = 0.955(2), Fe(sof) = 0.941(2), and Si(sof) = 0.939(2) (Madagascar); and <Ca–O> = 2.4344, Fe–O = 2.0156(8), Si–O = 1.6468(8) Å; Ca(sof) = 0.928(2), Fe(sof) = 0.908(2), and Si(sof) = 0.932(3) (Iran). The sofs based on the EMPA results are similar to those obtained from the Rietveld refinement. Each phase in the HRPXRD results can be correlated with a specific chemical composition. For example, the Iran sample composition Adr63Uv30 corresponds to phase-3 that has the smallest unit-cell parameter; Adr76Uv22 corresponds to phase-1 that has the intermediate cell value; and Adr86Uv13 corresponds to phase-2 that has the largest unit-cell parameter. The bond distances compare well with those obtained from radii sum. The three different cubic phases in each sample cause strain that arises from the mismatch of the cubic unit-cell parameters and give rise to birefringence.  相似文献   

2.
The macroscopically-zoned grandite from the garnetite skarn of Meka Presedla (Kopaonik Mountain, Serbia) was studied with optical microscopy, electron microprobe analysis (EMPA), Fourier transform infra-red (FT–IR), and Raman methods. The EMPA results indicate that the main core–rim compositional variations (Ca2.93–2.97Mn0.05–0.06Mg0.00–0.01Al1.14–1.26Fe3+0.72–0.83Ti0.00–0.02Si2.97–3.02O12) slightly differ along the zones, showing evidence for a quasi-cyclic alternation of the oscillatory zoning nature. Among this, considerable variation is observed only by the Al–Fe3+ substitutions in the octahedral site. The EMPA also indicate that the grandite zones compositionally vary, mostly within ±1 and ±2 mol% of the homogeneity level range, that is, Grs64±1Adr36±1Sps2 (A), Grs62±1Adr38±1Sps2 (B), Grs59±2Adr40±2Sps2 (C), Grs58±2Adr41±2Sps2 (D), and Grs58±1Adr41±1Sps2 (E). Therefore, the investigated garnet can be considered as relatively highly homogeneous. The majority of compositions lie within the narrow miscibility region of 0.58±2相似文献   

3.
The chemistry of garnet can provide clues to the formation of skarn deposits. The chemical analyses of garnets from the Astamal Fe-LREE distal skarn deposit were completed using an electron probe micro-analyzer. The three types of garnet were identified in the Astamal skarn are: (I) euhedral coarse-grained isotropic garnets (10–30 mm across), which are strongly altered to epidote, calcite and quartz in their rim and core, with intense pervasive retrograde alteration and little variation in the overall composition (Adr94.3–84.4 Grs8.5–2.7 Alm1.9–0.2) (garnet I); (II) anhedral to subhedral brecciated isotropic garnets (5–10 mm across) with minor alteration, a narrow compositional range along the growth lines (Adr82–65.4 Grs21.9–11.7 Alm11.1–2.4) and relatively high Cu (up to 1997 ppm) and Ni (up to 1283 ppm) (garnet II); and (III) subhedral coarser grained garnets (> 30 mm across) with moderate alteration, weak diffusion and irregular zoning of discrete grossular-almandine-rich domains (Adr84.2–48.8 Grs32.4–7.6 Alm19.9–3.5) (garnet III). In the third type, the almandine content increases with increasing grossular/andradite ratio and increasing substitutions of Al for Fe3 +.Almost all three garnet types have been replaced by fine-grained, dark-brown allanite that is typically disseminated and has the same relief as andradite. The Cu content increases while Ni content decreases slightly towards the rim of garnet II and garnet III. Copper in garnet II is positively correlated with increasing almandine content and decreasing andradite content, indicating that the almandine structure, containing relatively more Fe2 +, is more suitable than andradite and grossular to host divalent cations such as Cu2 +. Nickel in garnet II is positively correlated with increasing andradite content, total Fe, and decreasing almandine content. This is because Ni2 + substitutes for Fe3 + in the Y (octahedral) position. There are unusual discrete grossular-almandine rich domains within andraditic garnet III, indicating the low diffusivity of Ca compared to Fe at high temperatures.  相似文献   

4.
The crystal structure of a natural triclinic talc (1Tc polytype) [with composition: (Mg2.93Fe0.06)Σ2.99(Al0.02Si3.97)Σ3.99O10(OH)2.10] has been investigated by single-crystal X-ray diffraction at 223 and 170 K and by single-crystal neutron diffraction at 20 K. Both the anisotropic X-ray refinements (i.e. at 223 and 170 K) show that the two independent tetrahedra are only slightly distorted. For the two independent Mg-octahedra, the bond distances between cation-hydroxyl groups are significantly shorter than the others. The ditrigonal rotation angle of the six-membered ring of tetrahedra is modest (α ~ 4°). The neutron structure refinement shows that the hydrogen-bonding scheme in talc consists of one donor site and three acceptors (i.e. trifurcated configuration), all the bonds having O···O ≤ 3.38 Å, H···O ~ 2.8 Å, and O–H···O ~ 111–116°. The three acceptors belong to the six-membered ring of tetrahedra juxtaposed to the octahedral sheet. The vibrational regime of the proton site appears being only slightly anisotropic. The elastic behavior of talc was investigated by means of in situ synchrotron single-crystal diffraction up to 16 GPa (at room temperature) using a diamond anvil cell. No evidence of phase transition has been observed within the pressure range investigated. P–V data fit, with an isothermal third-order Birch-Murnaghan equation of state, results as follows: V 0 = 454.7(10) Å3, K T0 = 56(3) GPa, and K′ = 5.4(7). The “Eulerian finite strain” versus “normalized stress” plot yields: Fe(0) = 56(2) GPa and K′ = 5.3(5). The compressional behavior of talc is strongly anisotropic, as reflected by the axial compressibilities (i.e. β(a):β(b):β(c) = 1.03:1:3.15) as well as by the magnitude and orientation of the unit-strain ellipsoid (with ε 1:ε 2:ε 3 = 1:1.37:3.21). A comparison between the elastic parameters of talc obtained in this study with those previously reported is carried out.  相似文献   

5.
Two samples of hydroxyl-clinohumite, sample SZ0407B with approximate composition Mg8.674(14)Fe0.374(4)(Si0.99(1)O4)4(OH)2 and sample SZ0411B with composition Mg9(SiO4)4(OH)2, were synthesized at 12 GPa and 1,250 °C coexisting with olivine. Unit-cell parameters determined by single-crystal X-ray diffraction are given as follows: a = 4.7525(4) Å, b = 10.2935(12) Å, c = 13.7077(10) Å, α = 100.645(9)°, V = 659.04(9) Å3 for SZ0407B, and a = 4.7518(6) Å, b = 10.2861(12) Å, c = 13.7008(9) Å, α = 100.638(9)°, V = 658.15(9) Å3 for SZ0411B. Single-crystal X-ray intensity data were collected for crystal structure refinements of both samples. Relative to the pure-Mg sample, Fe decreases M3–OH bond lengths by ~0.010(3) Å, consistent with some ferric iron ordering into M3. Raman spectroscopy shows two strong bands in the lattice-mode region at 650 and 690 cm?1 in the Fe-bearing sample, which are not observed in the pure-Mg sample. Spectra in the H2O region show at least five bands, which are deconvolved into seven distinct O–H-stretching modes. Thermal expansion measurements were carried out for both samples from 153 to 787 K by single-crystal X-ray diffraction. The average a-, b-, c-axial and volumetric thermal expansion coefficients (10?6 K?1) are 10.5(1), 12.3(2), 12.5(2) and 34.9(5) for SZ0407B, respectively, and 11.1(1), 12.6(3), 13.7(3), 36.8(6) for SZ0411B, respectively. After heating, the unit-cell parameters were refined again for each sample at ambient condition, and no significant changes were observed, indicating no significant oxidation or dehydration during the experiment. For the DHMS phases along the brucite–forsterite join, linear regression gives a systematic linear decrease in expansivity with increasing density. Further, substitution of ferrous iron into these structures decreases thermal expansivity, making the Fe-bearing varieties slightly stiffer.  相似文献   

6.
The crystal structure and chemical composition of a crystal of (Mg14?x Cr x )(Si5?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 Mg13.66(8)Si4.70(6)Cr0.62(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   

7.
Lithian ferrian enstatite with Li2O = 1.39 wt% and Fe2O3 7.54 wt% was synthesised in the (MgO–Li2O–FeO–SiO2–H2O) system at P = 0.3 GPa, T = 1,000°C, fO2 = +2 Pbca, and a = 18.2113(7), b = 8.8172(3), c = 5.2050(2) Å, V = 835.79(9) Å3. The composition of the orthopyroxene was determined combining EMP, LA-ICP-MS and single-crystal XRD analysis, yielding the unit formula M2(Mg0.59Fe 0.21 2+ Li0.20) M1(Mg0.74Fe 0.20 3+ Fe 0.06 2+ ) Si2O6. Structure refinements done on crystals obtained from synthesis runs with variable Mg-content show that the orthopyroxene is virtually constant in composition and hence in structure, whereas coexisting clinopyroxenes occurring both as individual grains or thin rims around the orthopyroxene crystals have variable amounts of Li, Fe3+ and Mg contents. Structure refinement shows that Li is ordered at the M2 site and Fe3+ is ordered at the M1 site of the orthopyroxene, whereas Mg (and Fe2+) distributes over both octahedral sites. The main geometrical variations observed for Li-rich samples are actually due to the presence of Fe3+, which affects significantly the geometry of the M1 site; changes in the geometry of the M2 site due to the lower coordination of Li are likely to affect both the degree and the kinetics of the non-convergent Fe2+-Mg ordering process in octahedral sites.  相似文献   

8.
Babingtonite, Ca2Fe2+Fe3+[Si5O14(OH)] (Z?=?2, space group $ P\overline{1} $ ) from Yakuki mine (Japan), Grönsjöberget (Sweden), Kandivali Quarry (India), Baveno Quarry (Italy), Bråstad Mine (Norway), and Kouragahana (Japan), and manganbabingtonite, Ca2(Mn2+, Fe2+)Fe3+[Si5O14(OH)], from Iron Cap mine (USA) were studied using electron-microprobe analysis (EMPA), 57Fe Mössbauer analysis and single-crystal X-ray diffraction methods to determine the cation distribution at M1 and M2 and to analyze its effect on the crystal structure of babingtonite. Although all studied babingtonite crystals are relatively homogeneous, chemical zonation due to mainly Fe ? Mn substitution is observed in manganbabingtonite. Mössbauer spectra consist of two doublets with isomer shift (I.S.)?=?1.16–1.22 mm/s and quadrupole splitting (Q.S.)?=?2.33–2.50 mm/s and with I.S.?=?0.38–0.42 mm/s and Q.S.?=?0.82–0.90 mm/s, assigned to Fe2+ and Fe3+ at the M1 and M2 octahedral sites, respectively. The determined ratio of Fe2+/total Fe in manganbabingtonite (0.26) was smaller than that in the others (0.35–0.44) because of high Mn2+ content instead of Fe2+. The unit-cell parameters of babingtonite are a?=?7.466–7.478, b?=?11.624–11.642, c?=?6.681–6.690 Å, α?=?91.53–91.59, β?=?93.86–93.94, γ?=?104.20–104.34º, and V?=?560.2–562.3 Å3, and those of manganbabingtonite are a?=?7.4967(3), b?=?11.6632(4), c?=?6.7014(2) Å, α?=?91.602(2), β?=?93.989(2), γ?=?104.574(3)º, and V =565.09(5) Å3. Structural refinements converged to R 1 values of 1.64–3.16 %. The <M1-O> distance was lengthened due to the substitution of large octahedral cations such as Mn2+ for Fe2+. The increase of the M1-O8, M1-O8’ and M1-O13 lengths with mean ionic radii is slightly more pronounced than of the other M1-Oi lengths. The lengthened M1-O13 distance leads the positive correlation between Si5-O15-Si1 angle and M1-O13 distance. The increase of Si2-O3-Si1 and Si5-O12-Si4 angles due to the increase of mean ionic radius of M2 is also observed.  相似文献   

9.
High-pressure phase transitions of CaRhO3 perovskite were examined at pressures of 6–27 GPa and temperatures of 1,000–1,930°C, using a multi-anvil apparatus. The results indicate that CaRhO3 perovskite successively transforms to two new high-pressure phases with increasing pressure. Rietveld analysis of powder X-ray diffraction data indicated that, in the two new phases, the phase stable at higher pressure possesses the CaIrO3-type post-perovskite structure (space group Cmcm) with lattice parameters: a = 3.1013(1) Å, b = 9.8555(2) Å, c = 7.2643(1) Å, V m  = 33.43(1) cm3/mol. The Rietveld analysis also indicated that CaRhO3 perovskite has the GdFeO3-type structure (space group Pnma) with lattice parameters: a = 5.5631(1) Å, b = 7.6308(1) Å, c = 5.3267(1) Å, V m  = 34.04(1) cm3/mol. The third phase stable in the intermediate P, T conditions between perovskite and post-perovskite has monoclinic symmetry with the cell parameters: a = 12.490(3) Å, b = 3.1233(3) Å, c = 8.8630(7) Å, β = 103.96(1)°, V m  = 33.66(1) cm3/mol (Z = 6). Molar volume changes from perovskite to the intermediate phase and from the intermediate phase to post-perovskite are –1.1 and –0.7%, respectively. The equilibrium phase relations determined indicate that the boundary slopes are large positive values: 29 ± 2 MPa/K for the perovskite—intermediate phase transition and 62 ± 6 MPa/K for the intermediate phase—post-perovskite transition. The structural features of the CaRhO3 intermediate phase suggest that the phase has edge-sharing RhO6 octahedra and may have an intermediate structure between perovskite and post-perovskite.  相似文献   

10.
The nickel arsenide (B81) and related crystal structures are among the most important crystallographic arrangements assumed by Fe and Ni compounds with light elements such as Si, O, S, and P, expected to be present in planetary cores. Despite the simple structure, some of these materials like troilite (FeS) exhibit complex phase diagrams and rich polymorphism, involving significant changes in interatomic bonding and physical properties. NiP (oP16) represents one of the two principal structure distortions found in the nickel arsenide family and is characterized by P–P bonding interactions that lead to the formation of P2 dimers. In the current study, the single-crystal synchrotron X-ray diffraction technique, aided by first principles density functional theory (DFT) calculations, has been applied to examine the compression behavior of NiP up to 30 GPa. Two new reversible displacive phase transitions leading to orthorhombic high-pressure phases with Pearson symbols oP40 and oC24 were found to occur at approximately 8.5 and 25.0 GPa, respectively. The oP40 phase has the primitive Pnma space group with unit cell a = 4.7729(5) Å, b = 16.6619(12) Å, and c = 5.8071(8) Å at 16.3(1) GPa and is a superstructure of the ambient oP16 phase with multiplicity of 2.5. The oC24 phase has the acentric Cmc21 space group with unit cell a = 9.695(6) Å, b = 5.7101(9) Å, and c = 4.7438(6) Å at 28.5(1) GPa and is a superstructure of the oP16 phase with multiplicity of 1.5. DFT calculations fully support the observed sequence of phase transitions. The two new phases constitute logical next stages of P sublattice polymerization, in which the dilution of the P3 units, introduced in the first high-pressure phase, decreases, leading to compositions of Ni20(P3)4(P2)4 and Ni12(P3)4, and provide important clues to understanding of phase relations and transformation pathways in the NiAs family.  相似文献   

11.
The effects of temperature on the crystal structure of a natural epidote [Ca1.925 Fe0.745Al2.265Ti0.004Si3.037O12(OH), a = 8.890(6), b = 5.630(4), c = 10.150(6) Å and β = 115.36(5)°, Sp. Gr. P21 /m] have been investigated by means of neutron single-crystal diffraction at 293 and 1,070 K. At room conditions, the structural refinement confirms the presence of Fe3+ at the M3 site [%Fe(M3) = 73.1(8)%] and all attempts to refine the amount of Fe at the M(1) site were unsuccessful. Only one independent proton site was located. Two possible hydrogen bonds, with O(2) and O(4) as acceptors [i.e. O(10)–H(1)···O(2) and O(10)–H(1)···O(4)], occur. However, the topological configuration of the bonds suggests that the O(10)–H(1)···O(4) is energetically more favourable, as H(1)···O(4) = 1.9731(28) Å, O(10)···O(4) = 2.9318(22) Å and O(10)–H(1)···O4 = 166.7(2)°, whereas H(1)···O(2) = 2.5921(23) Å, O(10)···O(2) = 2.8221(17) Å and O(10)–H(1)···O2 = 93.3(1)°. The O(10)–H(1) bond distance corrected for “riding motion” is 0.9943 Å. The diffraction data at 1,070 K show that epidote is stable within the T-range investigated, and that its crystallinity is maintained. A positive thermal expansion is observed along all the three crystallographic axes. At 1,070 K the structural refinement again shows that Fe3+ share the M(3) site along with Al3+ [%Fe(M3)1,070K = 74(2)%]. The refined amount of Fe3+ at the M(1) is not significant [%Fe(M1)1,070K = 1(2)%]. The tetrahedral and octahedral bond distances and angles show a slight distortion of the polyhedra at high-T, but a significant increase of the bond distances compared to those at room temperature is observed, especially for bond distances corrected for “rigid body motions”. The high-T conditions also affect the inter-polyhedral configurations: the bridging angle Si(2)–O(9)–Si(1) of the Si2O7 group increases significantly with T. The high-T structure refinement shows that no dehydration effect occurs at least within the T-range investigated. The configuration of the H-bonding is basically maintained with temperature. However, the hydrogen bond strength changes at 1,070 K, as the O(10)···O(4) and H(1)···O(4) distances are slightly longer than those at 293 K. The anisotropic displacement parameters of the proton site are significantly larger than those at room condition. Reasons for the thermal stability of epidote up to 1,070 K observed in this study, the absence of dehydration and/or non-convergent ordering of Al and Fe3+ between different octahedral sites and/or convergent ordering on M(3) are discussed.  相似文献   

12.
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) Å3, 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 [(Mg0.5Cu0.5)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) Å3, is consistent with it being an enneahydrate [i.e. (Mg0.5Ni0.5)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) Å3, 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) Å3. 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   

13.
The crystal structures of natural jadeite, NaAlSi2O6, and synthetic kosmochlor, NaCrSi2O6, were studied at room temperature, under hydrostatic conditions, up to pressures of 30.4 (1) and 40.2 (1) GPa, respectively, using single-crystal synchrotron X-ray diffraction. Pressure–volume data have been fit to a third-order Birch–Murnaghan equation of state yielding V 0 = 402.5 (4) Å3, K 0 = 136 (3) GPa, and K 0 ′  = 3.3 (2) for jadeite and V 0 = 420.0 (3) Å3, K 0 = 123 (2) GPa and K 0 ′  = 3.61 (9) for kosmochlor. Both phases exhibit anisotropic compression with unit-strain axial ratios of 1.00:1.95:2.09 for jadeite at 30.4 (1) GPa and 1:00:2.15:2.43 for kosmochlor at 40.2 (1) GPa. Analysis of procrystal electron density distribution shows that the coordination of Na changes from 6 to 8 between 9.28 (Origlieri et al. in Am Mineral 88:1025–1032, 2003) and 18.5 (1) GPa in kosmochlor, which is also marked by a decrease in unit-strain anisotropy. Na in jadeite remains six-coordinated at 21.5 (1) GPa. Structure refinements indicate a change in the compression mechanism of kosmochlor at about 31 GPa in both the kinking of SiO4 tetrahedral chains and rate of tetrahedral compression. Below 31 GPa, the O3–O3–O3 chain extension angle and Si tetrahedral volume in kosmochlor decrease linearly with pressure, whereas above 31 GPa the kinking ceases and the rate of Si tetrahedral compression increases by greater than a factor of two. No evidence of phase transitions was observed over the studied pressure ranges.  相似文献   

14.
Hydrogen site positions and occupancy in the crystal structure of dense hydrous magnesium silicate (DHMS) phase E were determined for the first time by pulsed neutron powder diffraction. A fully deuterated pure phase E powder sample, which had space group \(R\overline{3} m\) and lattice parameters of a = 2.97065(8) Å and c = 13.9033(4) Å, was synthesized at 15 GPa and 1100 °C. Through quantitative evaluation of refined structure parameters obtained with sufficient spatial resolution and very high signal-to-background ratio, we conclude that the O–D dipoles in the refined phase E structure are tilted by 24° from the direction normal to the layers of edge-shared MgO6 octahedra (octahedral layers). The tilted dipole structure of phase E is in remarkable contrast to that of brucite, Mg(OH)2, which has dipoles exactly normal to the octahedral layer. This contrast exists because the O–Si–O bonding unique in the phase E structure connects two adjacent octahedral layers and thereby reduces the interlayer O···O distance. This shrinkage of the interlayer distance induces the tilting of the O–D dipole and also generates unique O–D···O hydrogen bonding connecting all the layers in the phase E structure.  相似文献   

15.
A new pyroxene with formula (Na0.86Mg0.14)(Mg0.57Ti0.43)Si2O6, synthesized in a high-pressure toroidal ‘anvil-with-hole’ apparatus at P = 7 GPa and T = 1700 °C, was characterized by X-ray single-crystal diffraction and Raman spectroscopy. The compound was found to be monoclinic (R1 = 2.56 %), space group C2/c, with lattice parameters a = 9.687(2), b = 8.814(1), c = 5.290(1) Å, β = 107.853(2)°, V = 430.08(1) Å3. The coexistence of Mg and Ti4+ at the M1 site does not induce strong modifications either to the M1 site or to the adjacent M2 site. The Raman spectrum of synthetic Na–Ti-pyroxene was obtained for the first time and compared with that of Mg2Si2O6 (with very low concentrations of Na and Ti). The structural characterization of the Na–Ti–Mg-pyroxene is important, because the study of its thermodynamic constants provides new constraints on thermobarometry of the upper mantle assemblages.  相似文献   

16.
The crystallographic structures of the synthetic cheralite, CaTh(PO4)2, and its homolog CaNp(PO4)2 have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO4 (Ln = La to Gd). The space group is P21/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO4)2 are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R wp = 4.87%, R p = 3.69% and R B = 3.99%. For CaNp(PO4)2, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R wp = 6.74%, R p = 5.23%, and R B = 6.05%. The results indicate significant distortions of bond length and angles of the PO4 tetrahedra in CaTh(PO4)2 and to a lesser extent in CaNp(PO4)2. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO4)2. A comparison with the isostructural compounds LnPO4 (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca2+ and Th4+ introduces a distortion of the PO4 tetrahedra.  相似文献   

17.
We have collected high resolution neutron powder diffraction patterns from Na2SO4·10D2O over the temperature range 4.2–300 K following rapid quenching in liquid nitrogen, and over a series of slow warming and cooling cycles. The crystal is monoclinic, space-group P21/c (Z = 4) with a = 11.44214(4) Å, b = 10.34276(4) Å, c = 12.75486(6) Å, β = 107.847(1)°, and V = 1436.794(8) Å3 at 4.2 K (slowly cooled), and a = 11.51472(6) Å, b = 10.36495(6) Å, c = 12.84651(7) Å, β = 107.7543(1)°, V = 1460.20(1) Å3 at 300 K. Structures were refined to R P (Rietveld powder residual, \( R_{P} = {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } \mathord{\left/ {\vphantom {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } {\sum {I_{\text{obs}} } }}} \right. \kern-\nulldelimiterspace} {\sum {I_{\text{obs}} } }} \)) better than 2.5% at 4.2 K (quenched and slow cooled), 150 and 300 K. The sulfate disorder observed previously by Levy and Lisensky (Acta Cryst B34:3502–3510, 1978) was not present in our specimen, but we did observe changes with temperature in deuteron occupancies of the orientationally disordered water molecules coordinated to Na. The temperature dependence of the unit-cell volume from 4.2 to 300 K is well represented by a simple polynomial of the form V = ? 4.143(1) × 10?7 T 3 + 0.00047(2) T2 ? 0.027(2) T + 1437.0(1) Å3 (R 2 = 99.98%). The coefficient of volume thermal expansion, α V , is positive above 40 K, and displays a similar magnitude and temperature dependence to α V in deuterated epsomite and meridianiite. The relationship between the magnitude and orientation of the principal axes of the thermal expansion tensor and the main structural elements are discussed; freezing in of deuteron disorder in the quenched specimen affects the thermal expansion, manifested most obviously as a change in the behaviour of the unit-cell parameter β.  相似文献   

18.
Omphacite is an important mineral component of eclogite. Single-crystal synchrotron X-ray diffraction data on natural (Ca, Na) (Mg, Fe, Al)Si2O6 omphacite have been collected at the Advanced Photon Source beamlines 13-BM-C and 13-ID-D up to 47 GPa at ambient temperature. Unit cell parameter and crystal structure refinements were carried out to constrain the isothermal equation of state and compression mechanism. The third-order Birch–Murnaghan equation of state (BM3) fit of all data gives V 0 = 423.9(3) Å3, K T0 = 116(2) GPa and K T0′ = 4.3(2). These elastic parameters are consistent with the general trend of the diopside–jadeite join. The eight-coordinated polyhedra (M2 and M21) are the most compressible and contribute to majority of the unit cell compression, while the SiO4 tetrahedra (Si1 and Si2) behave as rigid structural units and are the most incompressible. Axial compressibilities are determined by fitting linearized BM3 equation of state to pressure dependences of unit cell parameters. Throughout the investigated pressure range, the b-axis is more compressible than the c-axis. The axial compressibility of the a-axis is the largest among the three axes at 0 GPa, yet it quickly drops to the smallest at pressures above 5 GPa, which is explained by the rotation of the stiffest major compression axis toward the a-axis with the increase in pressure.  相似文献   

19.
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) [(K0.99Na0.05Ba0.01)(Mg2.60Al0.20Fe 0.21 2+ )[Si2.71Al1.29O10](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 ?/Å3). 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) Å3, K T0 = 44.5(24) GPa, and K′ = 8.0(9); (2) BM-EoS, V 0 = 747.0(3) Å3, 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   

20.
Cu-poor meneghinite from La Lauzière Massif (Savoy, France) has the composition (electron microprobe) (in wt%): Pb 59.50, Sb 20.33, Bi 1.19, Cu 0.87, Ag 0.05, Fe 0.03, S 17.62, Se 0.05, Total 99.64. Its crystal structure (X-ray on a single crystal) was solved with R1=0.0506, wR2=0.1026, with an orthorhombic symmetry, space group Pnma, and a=24.080(5) Å, b=4.1276(8) Å, c=11.369(2) Å, V=1130.0(4) Å3, Z=4. Relatively to the model of Euler and Hellner (1960), this structure shows a significantly lower site occupancy factor for the tetrahedral Cu site (0.146 against 0.25). Among the five other metallic sites, Bi appears in the one with predominant Sb. Developed structural formula: Cu0.15Pb2(Pb0.53Sb0.47)(Pb0.46Sb0.54)(Sb0.75Pb0.19Bi0.06)S6; the reduced one: Cu0.58Pb12.72(Sb7.04Bi0.24)S24. The formation of such a Cu-poor variety seems to be related to specific paragenetic conditions (absence of coexisting galena), or to crystallochemical constraints (minor Bi). To cite this article: Y. Moëlo et al., C. R. Geoscience 334 (2002) 529–536.  相似文献   

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