Crystal structures of iron bearing tetrahedrite and tennantite at 25 and 250°C by means of Rietveld refinement of synchrotron data

Rietveld refinement of X-ray synchrotron data was performed for two synthetic tetrahedrite samples, with 0.61 and 1.83 Fe atoms, and two synthetic tennantite samples with 0.10 and 1.23 Fe atoms p.f.u. M₁₂(Sb,As)₄S₁₃. Measurements were performed at 25 and 250°C. For both the phases, increased Fe substitution is reflected in the increased tetrahedral ‘Cu1’–S distance (‘Cu1’ is a site of Fe substitution) and Cu2–S distances. Cu2 was refined as a split position; the Cu2–Cu2 split about the plane of the S1₂S2 triangle is about 0.56 and 0.65 Å for tetrahedrite and tennantite, respectively. Cu2–Cu2 distances in the structure cavity are 2.8–2.9 Å. Between 25 and 250°C, the lattice parameter a increased by 0.02–0.04 Å and the interatomic distances by 0.01 Å on an average. Thermal expansion coefficients of little-substituted samples are similar to those of unsubstituted samples, whereas thermal expansion appears to decrease with increasing substitution by Fe. The Cu2–Cu2 split increases at 250°C by about 0.1 Å for tetrahedrite and by more than 0.15 Å for tennantite but the cage expansion is minimal so that the Cu2–Cu2 distances in the cavity decrease with temperature. Difference Fourier maps indicate that there is little residual electron density left between the two Cu2 half-sites in tetrahedrite but this inter-site density is substantially higher in tennantite. It increases with temperature, especially in the little-substituted tennantite sample.     

高铬刚玉：湖南沅水金刚石包裹体中发现的一种高压矿物

对湖南沅水金刚石中的包裹体矿物含铬刚玉进行了矿物学研究。确认合铬刚玉中铬的最高质量分数可达19．31％。根据EPMA分析,高铬刚玉的晶体化学分子式为（All683,Cro298,Fe0.010,Mn0．008,T10．0。4,Sb．001）2．0040s,获得了该样品的X射线粉末衍射图谱,并在此基础上进行了Rietve...     

CaPtO3 as a novel post-perovskite oxide

Structural, morphological, magnetic, and thermal properties have been investigated for a novel post-perovskite oxide CaPtO₃ synthesized under high pressure. By comparing obtained structural parameters with those for known post-perovskite compounds, we argue that the chemical bond has a strong covalent character. Precise measurements of the Langevin susceptibility χ ₀ = −9.6 × 10⁻⁵ emu/mol and Debye temperature θ ∼ 470 K provide a good opportunity to confirm the reliability of first-principle calculations on predicting physical properties of the Earth’s D” layer.     

Plagioclase preferred orientation by TOF neutron diffraction and SEM-EBSD

The lattice preferred orientation (LPO) of an anorthosite (composed of andesine) sampled from a highly deformed anorthositic mylonite (Grenville Province, Quebec) was measured by TOF neutron diffraction and SEM-EBSD. The quantitative texture analysis of neutron data was accomplished by using the Rietveld texture analysis with the WIMV algorithm, implemented in the program package Materials Analysis Using Diffraction (MAUD). The texture calculations of the EBSD data were performed by using the program BEARTEX. Analyses from neutron and electron diffraction data gave similar results if EBSD data are smoothed to account for grain statistics. The principal pole figures show (010) roughly parallel to the rock foliation, (001) poles exhibiting a low angle (25°) to the pole to foliation, and (100) poles close to the Y-direction (perpendicular to the lineation and foliation pole). The [100] crystallographic direction shows a maximum in the lineation direction, [010] directions concentrate near the foliation pole. The geological deformation conditions and the constructed pole figure patterns indicate that the preferred orientation could be attributed to intracrystalline slip dominantly on (010) with [100] as slip direction. Elastic properties, calculated by averaging, document weak anisotropy that has implications for the seismic structure of the lower crust.     

Behaviour of Fe-oxides relevant to contaminant uptake in the environment

The behaviour of Fe-oxides was investigated during precipitation and co-precipitation, phase transformation and dissolution, while their ability to adsorb and incorporate trace components was examined. Some samples were synthesised and studied under controlled laboratory conditions and other samples were taken from experiments designed to test the effectiveness of waste treatment strategies using iron. Surface-sensitive and high-resolution techniques were used to complement information gathered from classical, macroscopic methods.

Adsorption isotherms for Ni²⁺ uptake on synthetic ferrihydrite (Fe₅HO₈·4H₂O, often written simply Fe(OH)₃), goethite (-FeOOH), hematite (-Fe₂O₃) and magnetite (Fe₃O₄) were all similar, increasing as expected at higher pH. Desorption behaviour was also similar, but one third or more of the Ni²⁺ failed to return to solution. In the past, “irreversible sorption” has been blamed on uptake into micro-fractures or pores, but during examination (using Atomic force microscopy, AFM) of hundreds of Fe-oxide particles, no evidence for such features could be found, leading to the conclusion that Ni²⁺ must become incorporated onto or into the solids. When solutions of Fe(II) are oxidised in controlled laboratory conditions or during treatment of ash from municipal waste incinerators, two-line ferrihydrite forms rapidly and on never-dried samples, AFM shows abundant individual particles with diameter ranging from 0.5 to several tens of nanometers. Aging in solution at 70°C promotes growth of the particles into hematite and goethite and their identification (by X-ray powder diffraction, XRPD, with Rietveld refinement) becomes possible at the same aging stage as mineral morphology becomes recognisable by AFM. In other experiments that were designed to mimic natural attack by organic acids, colloidal lepidocrocite (γ-FeOOH) was observed in situ by AFM, while reductive dissolution removed material on specific crystal faces. Lath ends are eroded fastest while basal planes are more stable.

In order to help elucidate mechanisms of contaminant immobilisation by Fe-oxides, we examined samples from a reactive barrier made with 90% quartz sand, 5% bentonite and 5% zero-valent iron filings that had reacted with a solution typical of leachate from coal-burning fly ash using time-of-flight secondary ion mass spectroscopy (TOF-SIMS). Fe(0) oxidised to Fe(III), while soluble and toxic Cr(VI) was reduced to insoluble Cr(III). Chemical maps show Fe-oxide coatings on bentonite; Cr is associated with Fe-oxides to some extent but its association with Ca in a previously undescribed phase is much stronger. Other samples taken from municipal waste incinerator ash that had been treated by aeration in Fe(II) solutions were examined with transmission electron microscopy (TEM), selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDS). Pb and some Zn are seen to be dispersed throughout two-line ferrihydrite aggregates, whereas Sn and some Zn are incorporated simply as a result of entrainment of individual ZnSn-oxide crystallites.

Geochemical speciation models that fail to account for contaminant uptake in solid solutions within major phases or as thin coatings or entrained crystals of uncommon phases such as those described here risk to underestimate contaminant retardation or immobilisation.     

High-pressure phase transitions of CaRhO<Subscript>3</Subscript> perovskite

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.     

Rietveld analysis of a new high-pressure strontium silicate SrSi2O5

High-pressure synthesis of a new SrSi₂O₅ phase was performed at 16 GPa and 900°C by using a Kawai-type multianvil apparatus. The powder X-ray diffraction pattern of the compound was analyzed by Rietveld refinement based on the structure of a high-pressure polymorph of BaGe₂O₅, BaGe₂O₅ III. The structure is orthorhombic with space group Cmca and cell parameters of a = 5.2389(1) Å, b = 9.2803(2) Å, c = 13.4406(1) Å, V=653.46(2) Å ³ (Z=8, _calc=4.549 g/cm³). The structure consists of layers containing SiO₆ octahedra and SiO₄ tetrahedra. In a unit layer, oxygen and strontium atoms are arranged in an approximation to hexagonal close-packing. The strontium atom is accommodated in a 12-coordinated site. Each SiO₆ octahedron shares four corners with SiO₄ tetrahedra and the other two corners with another SiO₆ octahedra. The SiO₆ octahedra are linked to each other to form SiO₆ chains along the a-axis. This is the first known example of a silicate with a BaGe₂O₅ III-type structure.     

Measured and computed neutralization potentials from static tests of diverse rock types

Static tests typically are used in the initial stage of environmental assessments to predict the potential for acid mine drainage, and also are used to monitor waste disposal at active mining operations. The neutralization potential (NP) of 19 sedimentary, metamorphic, and igneous extrusive rocks was measured by the Sobek method to compare the results with those computed by using the quantitative mineralogy of the rocks and the NP values that were deemed to be appropriate for the individual minerals. Most of the computed NP values of the rocks are lower than the measured values, but a close relationship is evident. If the contents of carbonate minerals are low, the NP in non-ultramafic igneous rocks typically is controlled by the amount of Ca substitution in plagioclase, whereas in ultramafic rocks the NP contribution is dominated by the amount of olivine and serpentine. Compositional and NP analyses of plagioclase concentrates indicate that the NP systematically varies from <1 for the Na end-member to about 14 for compositions near that of the Ca end-member. Among several variables that can affect the Sobek NP values, the volume and normality of the acid added to the sample are well-known to influence the results; however, the temperature and duration of the acidification stage can also have a pronounced effect on the measured NP of some rocks, depending on their mineralogy. Fizz tests to estimate the carbonate content and the consequent acid addition are highly subjective, and the ‘no fizz’ rating is not to be taken literally. The NP results themselves provide a clear indication of whether a sample has been over-acidified or under-acidified in the test procedure.     

Distribution of Fe among octahedral sites and its effect on the crystal structure of pumpellyite

Two pumpellyites with the general formula W ₈ X ₄ Y ₈ Z ₁₂O_56-n (OH) _n were studied using ⁵⁷Fe Mössbauer spectroscopic and X-ray Rietveld methods to investigate the relationship between the crystal chemical behavior of iron and structural change. The samples are ferrian pumpellyite-(Al) collected from Mitsu and Kouragahana, Shimane Peninsula, Japan. Rietveld refinements gave Fe(X):Fe(Y) ratios (%) of 41.5(4):58.5(4) for the Mitsu pumpellyite and 46(1):54(1) for the Kouragahana pumpellyite, where Fe(X) and Fe(Y) represent Fe content at the X and Y sites, respectively. The Mössbauer spectra consisted of two Fe²⁺ and two Fe³⁺ doublets for the Mitsu pumpellyite, and one Fe²⁺ and two Fe³⁺ doublets for the Kouragahana pumpellyite. In terms of the area ratios of the Mössbauer doublets and the Fe(X):Fe(Y) ratios determined by the Rietveld refinements, Fe²⁺(X):Fe³⁺(X):Fe³⁺(Y) ratios are determined to be 22:14:64 for the Mitsu pumpellyite and 27:8:65 for the Kouragahana pumpellyite. By applying the Fe²⁺:Fe³⁺-ratio determined by the Mössbauer analysis and the site occupancies of Fe at the X and Y sites given by the Rietveld method together with chemical analysis, the resulting formula of the Mitsu and Kouragahana pumpellyites are established as Ca₈(Fe _0.88 ²⁺ Mg_0.68Fe _0.77 ³⁺ Al_1.66)_Σ3.99(Al_5.67Fe _2.34 ³⁺ )_Σ8.01Si₁₂O_42.41(OH)_13.59 and Ca₈(Mg_1.24Fe _0.65 ²⁺ Fe _0.46 ³⁺ Al_1.66)_Σ4.01(Al_6.71Fe _1.29 ³⁺ )_Σ8.00Si₁₂O_42.14(OH)_13.86, respectively. Mean Y–O distances and volumes of the YO₆ octahedra increase with increasing mean ionic radii, i.e., the Fe³⁺→Al substitution at the Y site. However, change of the sizes of XO₆ octahedra against the mean ionic radii at the X site is not distinct, and tends to depend on the volume change of the YO₆ octahedra. Thus, the geometrical change of the YO₆ octahedra with Fe³⁺→Al substitution at the Y site is essential for the structural changes of pumpellyite. The expansion of the YO₆ octahedra by the ionic substitution of Fe³⁺ for Al causes gradual change of the octahedra to more symmetrical and regular forms.