首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
Sized aggregates of glasses (47–84 wt% SiO2) were fused from igneous-derived cohesive fault rock and igneous rock, and step-heated from ~400 to >1,200 °C to obtain their 39Ar diffusion properties (average E=33,400 cal mol?1; D o=4.63×10?3 cm2 s?1). At T<~1,000 °C, glasses containing <~69 wt% SiO2 and abundant network-forming cations (Ca, Fe, Mg) reveal moderate to strong non-linear increases in D and E, reflecting structural modifications as the solid transitions to melt. Extrapolation of these Arrhenius properties down to typical geologic T-t conditions could result in a 1.5 log10 unit underestimation in the diffusion rate of Ar in similar materials. Numerical simulations based upon the diffusion results caution that some common geologic glasses will likely yield 40Ar/39Ar cooling ages rather than formation ages. However, if cooling rates are sufficiently high, ambient temperatures are sufficiently low (e.g., <65–175 °C), and coarse particles (e.g., radius (r) >~1 mm) are analyzed, glasses with compositions similar to ours may preserve their formation ages.  相似文献   

2.
To evaluate the impact of invading seagrass on biogeochemical processes associated with sulfur cycles, we investigated the geochemical properties and sulfate reduction rates (SRRs) in sediments inhabited by invasive warm affinity Halophila nipponica and indigenous cold affinity Zostera marina. A more positive relationship between SRR and below-ground biomass (BGB) was observed at the H. nipponica bed (SRR = 0.6809 × BGB ? 4.3162, r 2 = 0.9878, p = 0.0006) than at the Z. marina bed (SRR = 0.3470 × BGB ? 4.0341, r 2 = 0.7082, p = 0.0357). These results suggested that SR was more stimulated by the dissolved organic carbon (DOC) exuded from the roots of H. nipponica than by the DOC released from the roots of Z. marina. Despite the enhanced SR in spring-summer, the relatively lower proportion (average, 20%) of acid-volatile sulfur (AVS) in total reduced sulfur and the strong correlation between total oxalate-extractable Fe (Fe(oxal)) and chromium-reducible sulfur (CRS = 0.2321 × total Fe(oxal) + 1.8180, r 2 = 0.3344, p = 0.0076) in the sediments suggested the rapid re-oxidation of sulfide and precipitation of sulfide with Fe. The turnover rate of the AVS at the H. nipponica bed (0.13 day?1) was 2.5 times lower than that at the Z. marina bed (0.33 day?1). Together with lower AVS turnover, the stronger correlation of SRR to BGB in the H. nipponica bed suggests that the extension of H. nipponica resulting from the warming of seawater might provoke more sulfide accumulation in coastal sediments.  相似文献   

3.
The crystal structure of Pb6Bi2S9 is investigated at pressures between 0 and 5.6 GPa with X-ray diffraction on single-crystals. The pressure is applied using diamond anvil cells. Heyrovskyite (Bbmm, a = 13.719(4) Å, b = 31.393(9) Å, c = 4.1319(10) Å, Z = 4) is the stable phase of Pb6Bi2S9 at ambient conditions and is built from distorted moduli of PbS-archetype structure with a low stereochemical activity of the Pb2+ and Bi3+ lone electron pairs. Heyrovskyite is stable until at least 3.9 GPa and a first-order phase transition occurs between 3.9 and 4.8 GPa. A single-crystal is retained after the reversible phase transition despite an anisotropic contraction of the unit cell and a volume decrease of 4.2%. The crystal structure of the high pressure phase, β-Pb6Bi2S9, is solved in Pna2 1 (a = 25.302(7) Å, b = 30.819(9) Å, c = 4.0640(13) Å, Z = 8) from synchrotron data at 5.06 GPa. This structure consists of two types of moduli with SnS/TlI-archetype structure in which the Pb and Bi lone pairs are strongly expressed. The mechanism of the phase transition is described in detail and the results are compared to the closely related phase transition in Pb3Bi2S6 (lillianite).  相似文献   

4.
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   

5.
Acacia nilotica was used for the adsorption of Reactive Black 5 (RB5) dye from an aqueous solution. Both the raw and activated (with H3PO4) carbon forms of Acacia nilotica (RAN and ANAC, respectively) were used for comparison. Various parameters (including dye concentration, contact time, temperature, and pH) were optimized to obtain the maximum adsorption capacity. RAN and ANAC were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The maximum experimental adsorption capacities for RAN and ANAC were 34.79 and 41.01 mg g?1, respectively, which agreed with the maximum adsorption capacities predicted by the Langmuir, Freundlich, and Dubinin–Radushkevich equilibrium isotherm models. The adsorption data of ANAC showed a good fit to the isotherm models based on the coefficient of determination (R 2): Langmuir type II (R 2 = 0.99) > Freundlich (R 2 = 0.9853) > Dubinin–Radushkevich (R 2 = 0.9659). This result suggested monolayer adsorption of RB5 dye. The adsorption of RB5 dye followed pseudo-second-order kinetics. The RAN adsorbent reflected an exothermic reaction (enthalpy change, ΔH = ?0.006 kJ mol?1) and increased randomness (standard entropy change, ΔS = 0.038 kJ mol?1) at the solid–solution interface. In contrast, ANAC reflected both exothermic [?0.011 kJ mol?1 (303–313 K)] and endothermic [0.003 kJ mol?1 (313–323 K)] reactions. However, the ΔS value of ANAC was lower when the RB5 adsorption increased from 313 to 323 K. The negative values for the Gibbs free energy change at all temperatures indicated that the adsorption of RB5 dye onto RAN and ANAC was spontaneous in the forward direction.  相似文献   

6.
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) Å3, 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 (βa = 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 (βb = 0.016(2) GPa?1), K′ b = 10(2) for the b-axis; c 0 = 5.018(7) Å, K T0c = 33(3) GPa (βc = 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 CsAlSi5O12, 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   

7.
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   

8.
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   

9.
The main objective of this paper was to investigate the dewatering behaviour of a clayey uranium ore slurry. The slurry (containing 28% clay size) exhibited moderate water adsorption (w l  = 83% and w p  = 30%). Primarily composed of muscovite (46%) and quartz (30%), the clay minerals included illite (8%), chlorite (5%) and kaolinite (2%) alongside a CEC of 41 (cmol(+)/kg) with Ca2+ and Mg2+ as the dominant cations. Likewise, the high EC (17,600 μS/cm) and ionic strength (1.15 mol/L) indicated a flocculated microstructure due to the presence of SO4 2? (22,600 mg/L) and Mg2+ (1340 mg/L) in the slurry water. Settling included sedimentation and consolidation at low initial solids condition (25–35%) whereas only consolidation was observed at high initial solids contents (40–50%). The average k reduced from 1.2 × 10?6 m/s (initial s = 25%) to 5.3 × 10?8 m/s (initial s = 50%) along with a void ratio reduction from 7.4 to 2.6. Due to thixotropic strength, volume compressibility during consolidation showed apparent pre-consolidation at low effective stress (0.3–2 kPa) with a reduction in void ratio from 2.6 to 2.5. The e s was found to be 2.46 at σ′ = 2 kPa and was followed by a steeper slope with the void ratio reducing to 2.1 at σ′ = 31 kPa. Likewise, the hydraulic conductivity during consolidation decreased from 2.6 × 10?9 m/s (at e = 2.6) to 2.0 × 10?10 m/s (at e = 2.1).  相似文献   

10.
Using a diamond-anvil cell and synchrotron X-ray diffraction, the compressional behavior of a synthetic qandilite Mg2.00(1)Ti1.00(1)O4 has been investigated up to about 14.9 GPa at 300 K. The pressure–volume data fitted to the third-order Birch–Murnaghan equation of state yield an isothermal bulk modulus (K T0) of 175(5) GPa, with its first derivative \(K_{T0}^{{\prime }}\) attaining 3.5(7). If \(K_{T0}^{{\prime }}\) is fixed as 4, the K T0 value is 172(1) GPa. This value is substantially larger than the value of the adiabatic bulk modulus (K S0) previously determined by an ultrasonic pulse echo method (152(7) GPa; Liebermann et al. in Geophys J Int 50:553–586, 1977), but in general agreement with the K T0 empirically estimated on the basis of crystal chemical systematics (169 GPa; Hazen and Yang in Am Miner 84:1956–1960, 1999). Compared to the K T0 values of the ulvöspinel (Fe2TiO4; ~148(4) GPa with \(K_{T0}^{{\prime }} = 4\)) and the ringwoodite solid solutions along the Mg2SiO4–Fe2SiO4 join, our finding suggests that the substitution of Mg2+ for Fe2+ on the T sites of the 4–2 spinels can have more significant effect on the K T0 than that on the M sites.  相似文献   

11.
  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.
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   

14.
Undiluted reject water from the dewatering of anaerobic sludge with an average total nitrogen content of 718 ± 117 mg L?1 (n = 63) was used to start-up autotrophic nitrogen removal in three different pilot-scale (3 m3) deammonification configurations: (1) biofilm; (2) activated sludge sequence batch; and (3) two-staged (nitritation–anammox). Time- and concentration-based aeration control with alternating aerobic/anaerobic phases was applied for all reactor configurations. All reactors were initiated without anammox-specific inoculum, and biofilm was grown onto blank carriers. During the initial start-up period, biological nitrogen removal was found to be inhibited by an excessive free ammonia content (>10 mg-N L?1), resulting from the use of high-strength reject water as the process feed. After implementation of free ammonia control by pH adjustment to 6.5–7.5, propagation of the deammonification process was observed with increased nitrogen removal with slight accumulation of NO3 ?–N. The highest total nitrogen removal rates were achieved with the single-reactor biofilm- and sludge-based deammonification processes (1.04 and 0.30 kg-N m?3 day?1, respectively). The critical factors for successful start-up and stable operation of deammonification reactors turned out to be control of pH below 7.5, dissolved oxygen at 0.3–0.8 mg-O2 L?1 and influent solids values below 1000 nephelometric turbidity units. Microbial analysis demonstrated that highest anammox enrichment was achieved in the biofilm reactor (9.40 × 108 copies g?1 total suspended solids). These data demonstrate the potential of an in-situ grown sludge- or biofilm-based concept for the development and propagation of deammonification process.  相似文献   

15.
Single crystals of B2O3 are needed for the precise determination of the refractive indices used to calculate the electronic polarizability α of 3-coordinated boron. The α(B) values in turn are used to predict mean refractive indices of borate minerals. Since the contribution of boron to the total polarizability of a mineral is very low, the synthetic compound B2O3 represents an ideal model system because of its high molar content of boron. Millimeter-sized crystals were synthesized at 1 GPa in a piston-cylinder apparatus. The samples were heated above the liquidus (800 °C), subsequently cooled at 15 °C/h to 500 °C and finally quenched. The refractive indices were determined by the immersion method using a microrefractometer spindle stage. The refractive indices n o = 1.653 (3) and n e = 1.632 (3) correspond to a total polarizability for B2O3 of α = 4.877 Å3. These values were used to determine the electronic polarizability of boron of α(B) = 0.16 Å3. Although the surface of the B2O3 crystals was coated with a hydrous film immediately after being exposed to air, its bulk crystallinity is retained for a period of at least 2 months.  相似文献   

16.
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   

17.
  相似文献   

18.
A natural sample of clinochlore from the Longitudinal Valley area of northeastern Taiwan has been characterized by using the powder X-ray diffraction (XRD), differential thermal analysis and electron paramagnetic resonance (EPR) spectroscopic techniques. The lattice parameters of the monoclinic (IIb) clinochlore with the composition (Mg2.988 Al1.196 Fe1.6845 Mn0.026)5.8945 (Si2.559 Al1.441)4 O10 (OH)8 have been calculated from the powder XRD data and are found to be a = 5.347 Å, b = 9.223 Å, c = 14.250 Å, β = 97.2° and Z = 2. The thermal behaviour of the sample showed the typical behaviour of clinochlore with a hydroxyl content of 12.5 wt%. The EPR spectrum at room temperature exhibits two resonance signals centred at g ≈ 2.0 and g ≈ 8.0. The signal at g ≈ 2.0 shows a six-line hyperfine structure which is a characteristic of Mn2+ ions in octahedral symmetry. The resonance signal at g ≈ 8.0 is a characteristic of Fe3+ ions. The EPR spectra have also been recorded at different temperatures (123–295 K). The population of spin levels (N) has been calculated for g ≈ 2.0 and g ≈ 8.0 resonance signals. It is observed that N increases with decreasing temperature. From EPR spectra, the spin-Hamiltonian parameters have been evaluated. The zero-field splitting parameter (D) is found to be temperature dependent. The peak-to-peak width of the g ≈ 8.0 resonance signal is found to increase with decrease in temperature.  相似文献   

19.
The comparative compressibility and high-pressure stability of a natural epidote (0.79 Fe-total per formula unit, Fetot pfu) and clinozoisite (0.40 Fetot 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) Å3, K 0 = 115(2) GPa, and \(K_{0}^{'}\) = 3.7(2) for epidote and V 0 = 457.8(1) Å3, 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   

20.
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   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号