Electronic state of Fe2+ in (Mg,Fe)(Si,Al)O3 perovskite and (Mg,Fe)SiO3 majorite at pressures up to 81 GPa and temperatures up to 800 K

Despite a large number of studies of iron spin state in silicate perovskite at high pressure and high temperature, there is still disagreement regarding the type and P–T conditions of the transition, and whether Fe²⁺ or Fe³⁺ or both iron cations are involved. Recently, our group published results of a Mössbauer spectroscopy study of the iron behaviour in (Mg,Fe)(Si,Al)O₃ perovskite at pressures up to 110 GPa (McCammon et al. 2008), where we suggested stabilization of the intermediate spin state for 8- to 12-fold coordinated ferrous iron (^[8–12]Fe²⁺) in silicate perovskite above 30 GPa. In order to explore the behaviour in related systems, we performed a comparative Mössbauer spectroscopic study of silicate perovskite (Fe_0.12Mg_0.88SiO₃) and majorite (with two compositions—Fe_0.18Mg_0.82SiO₃ and Fe_0.11Mg_0.88SiO₃) at pressures up to 81 GPa in the temperature range 296–800 K, which was mainly motivated by the fact that the oxygen environment of ferrous iron in majorite is quite similar to that in silicate perovskite. The ^[8–12]Fe²⁺ component, dominating the Mössbauer spectra of majorites, shows high quadrupole splitting (QS) values, about 3.6 mm s^?1, in the entire studied P–T region (pressures to 58 GPa and 296–800 K). Decrease of the QS of this component with temperature at constant pressure can be described by the Huggins model with the energy splitting between low-energy e _g levels of ^[8–12]Fe²⁺ equal to 1,500 (50) cm^?1 for Fe_0.18Mg_0.82SiO₃ and to 1,680 (70) cm^?1 for Fe_0.11Mg_0.88SiO₃. In contrast, for the silicate perovskite dominating Mössbauer component associated with ^[8–12]Fe²⁺ suggests the gradual change of the electronic properties. Namely, an additional spectral component with central shift close to that for high-spin ^[8–12]Fe²⁺ and QS about 3.7 mm s^?1 appeared at ~35 (2) GPa, and the amount of the component increases with both pressure and temperature. The temperature dependence of QS of the component cannot be described in the framework of the Huggins model. Observed differences in the high-pressure high-temperature behaviour of ^[8–12]Fe²⁺ in the silicate perovskite and majorite phases provide additional arguments in favour of the gradual high-spin—intermediate-spin crossover in lower mantle perovskite, previously reported by McCammon et al. (2008) and Lin et al. (2008).     

Raman study of MgCr2O4–Fe2+Cr2O4 and MgCr2O4–MgFe2 3+O4 synthetic series: the effects of Fe2+ and Fe3+ on Raman shifts

Two synthetic series of spinels, MgCr₂O₄–Fe²⁺Cr₂O₄ and MgCr₂O₄–MgFe₂ ³⁺O₄ have been studied by Raman spectroscopy to investigate the effects of Fe²⁺ and Fe³⁺ on their structure. In the first case, where Fe²⁺ substitutes Mg within the tetrahedral site, there is a continuous and monotonic shift of the Raman modes A_1g and E_g toward lower wavenumbers with the increase of the chromite component into the spinel, while the F_2g modes remain nearly in the same position. In the second series, for low Mg-ferrite content, Fe³⁺ substitutes for Cr in the octahedral site; when the Mg-ferrite content nears 40 %, a drastic change in the Raman spectra occurs as Fe³⁺ starts entering the tetrahedral site as well, consequently pushing Mg to occupy the octahedral one. The Raman spectral region between 620 and 700 cm^?1 is associated to the octahedral site, where three peaks are present and it is possible to observe the Cr–Fe³⁺ substitution and the effects of order–disorder in the tetrahedral site. The spectral range at 500–620 cm^?1 region shows that there is a shift of modes toward lower values with the increase of the Mg-ferrite content. The peaks in the region at 200–500 cm^?1, when observed, show little or negligible Raman shift.     

Phase equilibria in the systems Fe2O3-MgO-TiO2 and FeO-MgO-TiO2 between 1173 and 1473 K, and Fe2+-Mg mixing properties of ilmenite, ferrous-pseudobrookite and ulvöspinel solid solutions

Detailed phase relations have been determined within the systems Fe₂O₃-MgO-TiO₂ and FeO-MgO-TiO₂. Experiments were performed over the temperature interval 1173–1473 K by equilibrating pelletized, fine-grained oxide mixtures in either inert calcia-stabilized zirconia pots (Fe₂O₃-MgO-TiO₂ system) or evacuated silica tubes (FeO-MgO-TiO₂ system). Equilibrium phase assemblages were determined by combined optical microscope, X-ray diffraction and EMP examination. Phase relations in the Fe₂O₃-MgO-TiO₂ ternary are dominated by the instability of the M₂O₃ solid solution relative to the phase assemblage M₃O₄ + M₃O₅. A miscibility gap along the M₂O₃ binary also gives rise to two, 3-phase fields (α-M₂O₃ + M₃O₅ + M₃O₄ and α′-M₂O₃ + M₃O₅ + M₃O₄) separated by the M₃O₄ + M₃O₅ phase field. Phase relations in the FeO-MgO-TiO₂ ternary were divided into two sub-systems. For the FeTiO₃-MgTiO₃-TiO₂ sub-ternary, there is complete solid solution along the M₂O₃ and M₃O₅ binary joins at high temperature. At low temperatures (T < 1373 K) the M₃O₅ pseudobrookite solid solution decomposes to M₂O₃ + TiO₂. Increasing the concentration of MgO in M₃O₅ phase results in a decrease in the temperature at which M₃O₅ becomes unstable and compositional tie lines linking M₂O₃ and TiO₂ fan out, before the appearance of a three-phase region where M₂O₃, M₃O₅, and TiO₂ coexist. Within the expanded FeO-MgO-TiO₂ system, at temperatures above ∼1273 K there is a continuous solid solution along the M₃O₄ binary. At low temperatures (T < 1273 K) the Mg₂TiO₄ end-member breaks down to MgO and MgTiO₃. The M₃O₄ phase shows significant non-stoichiometry, down to at least 1173 K. Fe²⁺-Mg partitioning data were obtained for coexisting M₂O₃-M₃O₅ and M₂O₃-M₃O₄ pairs in the FeO-MgO-TiO₂ ternary. Assuming a regular solution mixing model for all phases, the M₂O₃ and M₃O₄ solid solutions were both found to exhibit moderate positive deviations from ideality (∼2600 J/mol), whereas the data for the M₃O₅ binary suggest close to ideal behaviour. Received: 22 May 1998 / Accepted: 3 November 1998     

Co2+ in trigonal fields of oxygen based structures: Electronic absorption spectra of buetschliite-type K2Co(SeO3)2, K2Co2(SeO3)3 and zemannite-type K2Co2(SeO3)3 · 2H2O

Polarized single crystal absorption spectra, in the spectral range 40 000–5 000 cm^-1, were obtained on Co²⁺ in trigonally distorted octahedral oxygen fields of buetschliite-type K₂Co(SeO₃)₂ (I), K₂Co₂(SeO₃)₃ (II) and zemannite-type K₂Co₂(SeO₃)₃ · 2H₂O (III). Site symmetries of Co²⁺ are m (D_3d) in I, 3m (C_3v) in II, and 3 (C₃) in III. The spectra can be interpreted on the basis of an electric dipole mechanism, wherein transitions of Co²⁺ in the centrosymmetric site in I gain intensity from dynamic removal of the inversion centre by vibronic coupling. In accordance with the elongation of the CoO₆ octahedra along the trigonal axis, the split component E_(g) of the ground state ⁴T_1g in octahedral fields is the ground state in all three compounds. Trigonal field parameters Dq_(trig), D, D and the Racah parameters B have been fitted to the energies of spin allowed transitions (293 K) as follows: I: 744, 94, -16, and 838 cm^-1, resp.; II: 647, 227, 42, and 798 cm^-1, resp.; III: 667, 181, 21, and 809 cm^-1, respectively. Racah parameters C were estimated from the energy of some observed spin-forbidden transitions to be 3770 (I), 3280 (II), and 3465 cm^-1 (III). Values of Dq and of the Racah parameters B and C indicate slight differences of Co²⁺-O bonding in I as compared to II and III, with somewhat higher covalency in compounds II and III which contain face-sharing CoO₆ octahedra with short Co-Co contacts. Also, in II and III the observed D values do not agree with theoretical D values, predicted from the magnitude of the mean octahedral distortions.     

Ferrovalleriite, 2(Fe,Cu)S · 1.5Fe(OH)2: Validation as a mineral species and new data

Ferrovalleriite, ideally 2(Fe,Cu)S · 1.5Fe(OH)₂, a layered hydroxide-sulfide of the valleriite group and an analog of valleriite with Fe instead of Mg in the hydroxide block, has been approved by the IMA Commission on New Minerals, Nomenclature and Classification as a valid mineral species. It was found in the Oktyabr’sky Mine, Noril’sk, Krasnoyarsk krai, Siberia, Russia. Ferrovalleriite occurs in cavities of massive sulfide ore mainly consisting of cubanite and mooihoekite. In different cases, it is associated with magnetite, Fe-rich chlorite-like phyllosilicate, ferrotochilinite, hibbingite, or rhodochrosite. Ferrovalleriite forms crystals flattened on [001] (from scaly to tabular; up to 5 mm across and up to 0.3 mm thick), typically split and curved. Occasionally, they are combined into aggregates up to 1.5 × 2 cm. Ferrovalleriite is dark bronze-colored, with a metallic luster and black streak. The Mohs’ hardness is ca. 1; VHN is 35 kg/mm². Cleavage is perfect parallel to {001}, mica-like. Individuals are flexible and inelastic. D(calc) = 3.72 g/cm³. In reflected light, ferrovalleriite is pleochroic from yellowish to gray; bireflectance is moderate. Anisotropy is strong, with bluish gray to yellowish beige rotation colors. Reflectance values [R ₁–R ₂ %, (λ, nm)] are: 15.6–16.6 (470), 14.8–20.5 (546), 14.7–22.3 (589), 14.5–24.1 (650). The IR spectrum shows the presence of (OH) groups bonded with Fe cations and the absence of H2O molecules. The chemical composition of the holotype (wt %; electron microprobe, H content is calculated) is as follows: 0.10 Al, 0.03 Mn, 45.31 Fe, 0.07 Ni, 18.29 Cu, 20.37 S, 15.62 O, 0.98 H, total is 100.77. The empirical formula calculated on the basis of 2 S atoms is: Al_0.01Fe_2.55Cu_0.91S₂(OH)_3.07 = (Fe_1.09Cu_0.91)_Σ2S₂ · (Fe _1.34 ²⁺ Fe _0.12 ³⁺ Al_0.01)_Σ1.47(OH)_3.07. The structure of ferrovalleriite is incommensurate (misfit); two sublattices are present: (1) sulfide sublattice, space group $R\bar 3m$ , R3m or R32; the unit-cell dimensions are: a = 3.792(2), c = 34.06(3) Å, V = 424(1) ų and (2) hydroxide sublattice, space group $P\bar 3m1$ , P3m1 or P321; the unit-cell dimensions: a = 3.202(3), c = 11.35(2)Å, V = 100.8(3) ų. Together with this main polytype modification with three-layer (R-cell, Z = 3) sulfide block, the holotype ferrovalleriite contains the modification with one-layer (P-cell, Z = 1) sulfide block (sulfide sublattice with $P\bar 3m1$ , P3m1 or P321, unit cell dimensions: a = 3.789(4), c = 11.35(1) Å, V = 141(5) ų). The strongest reflections in the X-ray powder pattern (d, Å-I) are: 5.69–100; 3.268–58; 3.163–36; 1.894–34; 1.871–45.     

Haitaite-(La), LaU4+Fe3+2(Ti13Fe2+4Fe3+)Σ18O38, a New Member of the Crichtonite Group

Haitaite-(La), (La, Ce)(U4+, U6+, Fe2+)(Fe3+, Al)2(Ti, Fe2+, Fe3+)18O38, is a new member of the crichtonite group. It is named after the Haita Village in the Miyi County of Sichuan Province, China, where the mineral was discovered. The mineral occurs as black opaque centimeter-sized aggregates in the external contact zone between the Neoproterozoic (~800 Ma) alkali feldspar granite and the Mesoproterozoic (~1700 Ma) micaschist. In the studied sample, haitaite-(La) is associated with other minerals, including ilmenite, magnetite, rutile, zircon, brannerite and uraninite. The new mineral is a black, metallic phase and has a Mohs hardness of 6, with a density of 4.99 g/cm3 (calculated) and 5.03 g/cm3 (measured). Haitaite-(La) is opaque in transmitted light and grayish-white under reflected light, with a reflectivity between 22.5% and 16.42% in the 400–700 nm band (SiC, in the air). The compositions of the mineral were measured by EPMA, the U4+/U6+ ratio was determined by X-ray photoelectron spectroscopy and the Fe2+/Fe3+ ratio was determined by M?ssbauer spectroscopy. Haitaite-(La) is trigonal, belongs to R3ˉ and has unit-cell parameters a = 10.3678(5) ?, c = 20.8390(11) ?, V = 1939.9(2) ?3, Z = 3. The crystalline structure is composed of octahedra with 9 layers of close-packed octahedra (M1, M3, M4, M5), tetrahedra (M2) and contains large 12-coordinated M0 sites.     

西藏中尼公路(K4770+500～K4771+200段)卡如滑坡研究

中尼公路是联结西藏与内地,西藏与尼泊尔的重要交通要道。自通车以来,K4770 500~K4771 200段一直受到滑坡的影响,威胁着交通及行人安全。论文通过系统分析,阐述了滑坡形成的机理。并通过数值模拟和计算,为滑坡的稳定性进行了分析和计算,为滑坡的治理提供了理论依据。     

Zemannite-type Selenites: Crystal structures of K2[CO2(SeO3)3] · 2H2O and K2[Ni2(SeO3)3] · 2H2O

Summary Crystals of K₂[Co₂(SeO₃)₃]-2H₂O and K₂[Ni₂(SeO₃)₃]-2H₂O were synthesized under low-hydrothermal conditions. Their structures were determined using single crystal X-ray data up to sin / = 0.7Å^-1. [Space group P6₃/m; a = 9.091(3),9.016(2)Å; c = 7.562(2), 7.476(2)Å; Z = 2; R_W = 1.6, 2.5%]. The investigations confirmed that K₂[Co₂(SeO₃)₃].2H₂O and K₂[Ni₂(SeO₃)₃]-2H₂O represent the first selenites belonging to the zemannite structure type, a framework structure with wide channels running parallel [0001]. In both compounds four maxima were clearly located in the channel by Fourier summations and attributed to two K atoms and two H₂O molecules, each with an occupancy factor of 1/6; a possible ordering scheme (full occupancy) with local symmetry 1 and [6]-coordinated K atoms could be derived for the channel atoms.Zusammenfassung Kristalle von K₂[Co₂(SeO₃)₃]-2H₂O und K₂[Ni₂(SeO₃)₃]-2H₂O wurden unter niedrig-hydrothermalen Bedingungen synthetisiert. Die Strukturen wurden unter Verwendung von Einkristallröntgendaten bis sin /= 0.7Å^-1 bestimmt. [Raumgruppe P6₃/m; a = 9.091(3), 9.016(2)Å; c = 7.562(2), 7.476(2)Å; Z = 2; R_W = 1.6, 2.5%] Die Untersuchungen bestätigten, daß K2[Co₂(SeO₃)₃] - 2H₂O und K₂ [Ni₂(SeO₃)₃] - 2H₂O als erste Selenite dem Strukturtyp des Zemannits angehören, einer Gerüststruktur mit weiten, parallel [0001] verlaufenden Kanälen. In beiden Verbindungen wurden im Kanal vier Maxima durch Fourier-Summationen eindeutig lokalisiert und zwei Kalium-atomen sowie zwei H₂O Molekülen, jeweils mit einem Besetzungsfaktor von 1/6, zugeschrieben. Für die Kanalatome konnte ein möglicher Ordnungszustand (volle Besetzung) mit lokaler Symmetrie 1 und [6]-koordinierten Kaliumatomen abgeleitet werden.

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Selenite des Zemannittyps: Kristallstrukturen von K₂[Co₂(SeO₃)₃] - 2H₂O und K₂[Ni₂(SeO₃)₃]-2H₂O

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Dedicated to Prof. Dr. Josef Zemann at the occasion of his 70^th birthday

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With 2 Figures     

Experimental study of the K2ZrSi3O9 (wadeite)–K2TiSi3O9 and K2(Zr,Ti)Si3O9–phlogopite systems at 2–3 GPa

Experiments ranging from 2 to 3 GPa and 800 to 1300 °C and at 0.15 GPa and 770 °C were performed to investigate the stability and mutual solubility of the K₂ZrSi₃O₉ (wadeite) and K₂TiSi₃O₉ cyclosilicates under upper mantle conditions. The K₂ZrSi₃O₉–K₂TiSi₃O₉ join exhibits complete miscibility in the P–T interval investigated. With increasing degree of melting the solid solution becomes progressively enriched in Zr, indicating that K₂ZrSi₃O₉ is the more refractory end member. At 2 GPa, in the more complex K₂ZrSi₃O₉–K₂TiSi₃O₉–K₂Mg₆Al₂Si₆O₂₀(OH)₄ system, the presence of phlogopite clearly limits the extent of solid solution of the cyclosilicate to more Zr-rich compositions [Zr/(Zr + Ti) > 0.85], comparable to wadeite found in nature, with TiO₂ partitioning strongly into the coexisting mica and/or liquid. However, at 1200 °C, with increasing pressure from 2 to 3 GPa, the partitioning behaviour of TiO₂ changes in favour of the cyclosilicate, with Zr/(Zr + Ti) of the K₂(Zr,Ti)Si₃O₉ phase decreasing from ∼0.9 to ∼0.6. The variation in the Ti content of the coexisting phlogopite is related to its degree of melting to forsterite and liquid, following the major substitution ^VITi+^VI□=2^VIMg. Received: 26 January 1999 / Accepted: 10 January 2000     

离子交换-比色法测定农业地质普查样品中的微量碘(Fe3+-CNS--NO-2)

本文采用离子交换-比色法测定农业地质样品中的微量碘,本方法检出限为0.5×10-6,精密度达到2.4%.方法准确、快速、简便、成本低,适合大批量样品的测定.     

Fe(II) reduction of pyrolusite (β-MnO<Subscript>2</Subscript>) and secondary mineral evolution

Iron (Fe) and manganese (Mn) are the two most common redox-active elements in the Earth’s crust and are well known to influence mineral formation and dissolution, trace metal sequestration, and contaminant transformations in soils and sediments. Here, we characterized the reaction of aqueous Fe(II) with pyrolusite (β-MnO₂) using electron microscopy, X-ray diffraction, aqueous Fe and Mn analyses, and ⁵⁷Fe Mössbauer spectroscopy. We reacted pyrolusite solids repeatedly with 3 mM Fe(II) at pH 7.5 to evaluate whether electron transfer occurs and to track the evolving reactivity of the Mn/Fe solids. We used Fe isotopes (56 and 57) in conjunction with ⁵⁷Fe Mössbauer spectroscopy to isolate oxidation of Fe(II) by Fe(III) precipitates or pyrolusite. Using these complementary techniques, we determined that Fe(II) is initially oxidized by pyrolusite and that lepidocrocite is the dominant Fe oxidation product. Additional Fe(II) exposures result in an increasing proportion of magnetite on the pyrolusite surface. Over a series of nine 3 mM Fe(II) additions, Fe(II) continued to be oxidized by the Mn/Fe particles suggesting that Mn/Fe phases are not fully passivated and remain redox active even after extensive surface coverage by Fe(III) oxides. Interestingly, the initial Fe(III) oxide precipitates became further reduced as Fe(II) was added and additional Mn was released into solution suggesting that both the Fe oxide coating and underlying Mn phase continue to participate in redox reactions when freshly exposed to Fe(II). Our findings indicate that Fe and Mn chemistry is influenced by sustained reactions of Fe(II) with Mn/Fe oxides.

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Structure and stability of the Fe(II)–Fe(III) green rust “fougerite” mineral and its potential for reducing pollutants in soil solutions

Fe(II)–Fe(III) layered double hydroxysalt green rusts, GRs, are very reactive compounds with the general formula, [Fe^II_(1−x) Fe^III_x (OH)₂]^x+·[(x/n) Aⁿ⁻·(m/n) H₂O]^x−, where x is the ratio Fe^III/Fe_tot, and reflects the structure in which brucite-like layers alternate with interlayers of anions Aⁿ⁻ and water molecules. Two types of crystal structure for GRs, GR1 and GR2, represented by the hydroxychloride GR1(Cl⁻) and the hydroxysulphate GR2(SO₄²⁻) are distinguished by X-ray diffraction due to different stacking. By analogy with GR1(Cl⁻) the structure of the fougerite GR mineral, [Fe^II_(1−x) Fe^III_x (OH)₂]^x+·[x OH⁻·(1−x) H₂O]^x-  Fe(OH)_(2+x)·(1−x) H₂O, is proposed displaying interlayers made of OH⁻ ions and water molecules (in situ deprotonation of water molecules is necessary for explaining the flexibility of its composition). The space group of mineral GR1(OH⁻) would be R3̄m, with lattice parameters a≅0.32 and c≅2.25 nm. Stability conditions and the E_h-pH diagram of Fe(OH)_(2+x) (the water molecules are omitted) are determined from hydromorphic soil solution equilibria with GR mineral in Brittany (France). Computed Gibbs free energies of formation from soil solution/mineral equilibrium fit well with a regular solid solution model: μ°[Fe(OH)_(2+x)]=(1−x) μ°[Fe(OH)₂]+x μ°[Fe(OH)₃]+RT [(1−x) ln (1−x)+x ln x]+A₀ x (1−x), where μ°[Fe(OH)₂]=−492.5 kJ mol⁻¹, μ°[Fe(OH)₃]=−641 kJ mol⁻¹ and A₀=−243.9 kJ mol⁻¹ at the average temperature of 9±1°C. The upper limit of occurrence of GR mineral at x=2/3, i.e. Fe₃(OH)₈, is explained by its unstability vs. α-FeOOH and/or magnetite; Fe(OH)₃ is thus a hypothetical compound with a GR structure which cannot be observed. These thermodynamic data and E_h-pH diagrams of Fe(OH)_(2+x) can be used most importantly to predict the possibility that GR minerals reduce some anions in contaminated soils. The cases of NO₃⁻, Se(VI) or Cr(VI) are fully illustrated.     

低温绿泥石成分温度计Fe/(Fe+Mg)校正的必要性问题

绿泥石是沉积岩、低级变质岩和水热蚀变岩中的常见矿物,基于四次配位Al含量的绿泥石成分温度计是确定古成岩或变质温度的最主要的手段之一。介绍了四种应用最为广泛的绿泥石成分温度计的原理,并从离子替代规律和比较研究的角度着重讨论了近年来关于绿泥石成分温度计校正的必要性。研究表明,在铝饱和的条件下,根据绿泥石中的Fe/(Fe Mg)值对绿泥石温度计进行校正并不能使计算值与实际值更为接近,而且从晶体化学的角度看,全岩的Fe/(Fe Mg)主要影响的是绿泥石中六次配位Fe与Mg的占位,而且偶合置换(Si4 )Ⅳ(Mg2 )Ⅵ—(Al3 )Ⅳ(Al3 )Ⅵ和(Si4 )Ⅳ(Fe2 )Ⅵ—(Al3 )Ⅳ(Al3 )Ⅵ共同控制着四次配位Al的占位。所以在铝饱和的岩石体系中可不必进行Fe/(Fe Mg)值的校正。     

三(明)-福(州)高速公路K196+425～+640段路堑右侧边坡滑坡治理

三(明)-福(州)高速公路三明段为国道G104主干线京-福高速公路在福建省三明市境内的一期工程。是一条在山岭重丘区修建的高速公路。三-福高速公路三明段SA7合同段K196 425~ 640段路堑右侧边坡原设计为6级半高边坡,并在第2和第3级设计了锚索地梁锚固。待施工至第1级时,高边坡产生较大规模滑坡,估计体积约12.5万m3。滑坡产生的主要原因是坡体工程地质和水文地质条件差。其次是源于区内连续降雨。再其次是设计锚固深度不足。后经中铁西北科学研究院论证制定了一套较完整的包括刷方减载、放缓边坡、加宽平台、分台整治、预应力锚索框架加固、仰斜坡体排水孔疏水以及地表完善的截排水系统等综合治理方案。所有加固工程完成后,在该高边坡共布置监测断面6条。至今已分别进行了4次深孔位移监测,并经1a多的检验,治理效果良好。     

红河石Ca18(□,Ca)2Fe2+Al4(Fe3+,Mg,Al)8(□,B)4BSi18O69(O,OH)9——符山石族新矿物

作为符山石族矿物的新成员,红河石(Hongheite,IMA 2017-027新矿物),Ca18(,Ca)2Fe2+Al4(Fe3+,Mg,Al)8(,B)4BSi18O69(O,OH)9发现于个旧世界级Sn-多金属矿田东北缘、与马拉格Sn矿床毗邻的北沙冲花岗岩(77.43Ma)内矽卡岩中。红河石常呈横径达4~25mm的放射状针-柱状集合体产出。当位于晶洞中时,红河石则呈发育良好的自形柱状晶体(0.5~4.0mm长,0.3~1.0mm宽)产出。与红河石共生的矿物见有赛黄晶、萤石、斧石-(Fe)、硅硼钙石、枪晶石、硼锡钙石、石英和羟鱼眼石-(K)等。红河石为墨绿色,条痕浅灰绿色,玻璃光泽,性脆,断口不规则。主要的晶面是:{100}、{110}、{101}和{001}。红河石的显微硬度:988.3N/mm2,相当于摩氏硬度6~7。其实测密度与计算密度分别是3.446g/cm3和3.423g/cm3。红河石一轴正晶,No=1.720(2),Ne=1.725(2);多色性弱。红河石的化学成分:SiO235.85%;TiO20.01%;Al2O311.00%;Fe2O37.92%;FeO2.14%;CaO 33.57%;MnO 0.42%;MgO 3.48%;B2O32.82%;Cr2O30.01%;Na2O 0.01%;F 0.40%(F≡O-0.17);Cl 0.14%(Cl≡O-0.03);H2O 0.75%,总量98.32%。依据晶体结构精测和Si在单位分子式中的原子数(即Si=18 apfu),计算和书写的红河石简化晶体化学式:Ca18(,Ca)2Fe2+Al4(Fe3+,Mg,Al)8(,B)4BSi18O69(O,OH)9。其三条最强粉晶线[d(?)(I/I0)(hkl)]为:2.9289(47)(004),2.7661(100)(342)和2.6079(68)(243)。红河石属四方晶系,空间群为P4/nnc,晶胞参数:a=15.667(3)?,c=11.725(1)?,V=2878(1)?3,Z=2。红河石晶体结构精测的R因子为0.063。红河石殊异于为已知的符山石族矿物种,在于其X(4)位以空位()为主、Y(3)位以Fe3+居优和T(2)位被B所占。顺便对符山石族矿物晶体-化学式的计算与书写予以讨论并提出建议。     

Fe(Ⅲ)水解过程中的Fe同位素分馏研究

三价铁水解是铁地球化学循环中的一个重要过程,在一定程度上控制了铁在水体中的运移和再分配。实验研究了Fe(Ⅲ)在20℃和46℃水解生成沉淀过程中,上清液的存在形态以及该过程导致的Fe同位素分馏。20℃水解实验有两个时间长度,分别是95天和130天,水解实验结束时上清液中的Fe(Ⅲ)主要以胶体形式存在。不同的水解时间导致的Fe同位素分馏在误差范围内是一致的。20℃水解实验结束时上清液和沉淀之间56Fe/54Fe的同位素组成之间的差异Δ56FeFe(Ⅲ)sup-Fe(Ⅲ)pre为1.15‰;46℃水解实验的时间长度为95天,结束时上清液中的Fe(Ⅲ)主要以离子形式存在,46℃水解实验结束时Δ56FeFe(Ⅲ)sup-Fe(Ⅲ)pre为1.37‰。通过瑞利分馏的公式计算出20℃和46℃时Fe(Ⅲ)水解过程中沉淀和上清液间的瞬时平衡分馏系数分别为0.999 121和0.999 260。     

Fe–Mg Interdiffusion in (Mg,Fe)O

We have performed a series of interdiffusion experiments on magnesiowüstite samples at room pressure, temperatures from 1,320° to 1,400°C, and oxygen fugacities from 10^?1.0 Pa to 10^?4.3 Pa, using mixed CO/CO₂ or H₂/CO₂ gases. The interdiffusion couples were composed of a single-crystal of MgO lightly pressed against a single-crystal of (Mg_1-x Fe _x )_1-δO with 0.07<x<0.27. The interdiffusion coefficient was calculated using the Boltzmann–Matano analysis as a function of iron content, oxygen fugacity, temperature, and water fugacity. For the entire range of conditions tested and for compositions with 0.01<x<0.27, the interdiffusion coefficient varies as $$\tilde D\, =\,2.9\times10^{ - 6}\,f_{{\text{O}}_2 }^{0.19}\,x^{0.73}\,{\text{e}}^{ - (209,000\, -\,96,000\,x)/RT}\,\,{\text{m}}^{\text{2}} {\text{s}}^{ -1} $$ These dependencies on oxygen fugacity and composition are reasonably consistent with interdiffusion mediated by unassociated cation vacancies. For the limited range of water activity that could be investigated using mixed gases at room pressure, no effect of water on interdiffusion could be observed. The dependence of the interdiffusion coefficient on iron content decreased with increasing iron concentration at constant oxygen fugacity and temperature. There is a close agreement between our activation energy for interdiffusion extrapolated to zero iron content (x=0) and that of previous researchers who used electrical conductivity experiments to determine vacancy diffusivities in lightly doped MgO.     

Hydrogen bonding in coquimbite, nominally Fe2(SO4)3·9H2O, and the relationship between coquimbite and paracoquimbite

Using single-crystal X-ray diffraction at 293, 200 and 100 K, and neutron diffraction at 50 K, we have refined the positions of all atoms, including hydrogen atoms (previously undetermined), in the structure of coquimbite ( $ P {\bar 3}1c $ , a?=?10.924(2)/10.882(2) Å, c?=?17.086(3) / 17.154(3) Å, V?=?1765.8(3)/1759.2(5) ų, at 293 / 50 K, respectively). The use of neutron diffraction allowed us to determine precise and accurate hydrogen positions. The O–H distances in coquimbite at 50 K vary between 0.98 and 1.01 Å. In addition to H₂O molecules coordinated to the Al³⁺ and Fe³⁺ ions, there are rings of six “free” H₂O molecules in the coquimbite structure. These rings can be visualized as flattened octahedra with the distance between oxygen and the geometric center of the polyhedron of 2.46 Å. The hydrogen-bonding scheme undergoes no changes with decreasing temperature and the unit cell shrinks linearly from 293 to 100 K. A review of the available data on coquimbite and its “dimorph” paracoquimbite indicates that paracoquimbite may form in phases closer to the nominal composition of Fe₂(SO₄)₃·9H₂O. Coquimbite, on the other hand, has a composition approximating Fe_1.5Al_0.5(SO₄)₃·9H₂O. Hence, even a “simple” sulfate Fe_2-x Al _x (SO₄)₃·9H₂O may be structurally rather complex.     

Fe3+ -SiO2-TiO2薄膜的制备及其光催化活性

Sol-gel法制备Fe3 掺杂TiO2催化剂的基础上,掺入SiO2纳米粉体,制备了一种改性Fe3 -SiO2-TiO2薄膜。以甲醛为降解对象,探讨金属掺杂和半导体复合量、活化温度、负载量等对该薄膜光催化活性的影响。结果表明,在500℃焙烧、质量比Fe3 ∶SiO2∶TiO2=1.0∶12∶100、镀膜5层时,Fe3 -SiO2-TiO2薄膜的光催化活性最高,150min后甲醛降解率达93%,是单纯TiO2薄膜的1.9倍。