Pressure-induced amorphization of A-site-deficient double perovskite Ln1/3MO3 (Ln = Pr,Nd, M = Nb,Ta)

High-pressure X-ray diffraction measurements have demonstrated that the cation-deficient perovskites Pr_1/3NbO₃, Pr_1/3TaO₃, Nd_1/3NbO₃, and Nd_1/3TaO₃ undergo irreversible pressure-induced amorphization (PIA). This occurs near 14.5 GPa for the niobates and 18.5 GPa for the tantalates. The unit cell volumes of the four oxides show an almost linear decrease as the pressure is increased. It is concluded that the PIA transition occurs at higher pressures in the tantalates due to the lower MO₆ initial tilting at ambient conditions, which is associated with the larger atomic mass of the tantalum. The behavior of these oxides is compared to that of CaTiO₃, and the role of both the weakening of the M–O–M π-bonding and the cation vacancies on the observed structural changes is discussed.     

化学共沉淀法制备小颗粒红色荧光粉(Y,Gd)BO3∶Eu3+

为了满足彩色等离子体平板显示(PDP)用荧光粉的要求,采用化学共沉淀法并结合超声波分散技术制备PDP用(Y,Gd)BO3∶Eu3 红色荧光粉.在稀土离子浓度、烧结温度等实验的基础上,得到分子式为(Y0.85Gd0.1)BO3∶Eu0.05、烧结温度为1 000℃的最佳实验方案.同时选择了不同的分散试剂并结合超声波分散技术对样品进行了后处理实验.结果表明:当分散试剂为乙醇时,样品的相对发光强度最高;同时,采用后处理试剂并结合超声波分散技术对样品进行后处理大大降低了粉体的团聚现象并增强了粉体的分散性,提高了粉体的质量.与传统的固相法相比,此法不仅大大降低了合成温度,同时,粉体的质量比固相法合成的要好,粉体的亮度高(以国外红粉为参考),样品经后处理后,颗粒细小、均匀,粒径分布约为300 nm.     

Thermodynamic properties of tooeleite,Fe63+(As3+O3)4(SO4)(OH)4·4H2O

Tooeleite, nominally Fe₆³⁺(As³⁺O₃)₄(SO₄)(OH)₄·4H₂O, is a relatively uncommon mineral of some acid-mine drainage systems. Yet, if it does occur, it does so in large quantities, indicating that some specific conditions favor the formation of this mineral in the system Fe-As-S-O-H. In this contribution, we report the thermodynamic properties of synthetic tooeleite. The sample was characterized by powder X-ray diffraction, scanning electron microscopy, extended X-ray absorption fine-structure spectroscopy, and Mössbauer spectroscopy. These methods confirmed that the sample is pure, devoid of amorphous impurities of iron oxides, and that the oxidation state of arsenic is 3+. Using acid-solution calorimetry, the enthalpy of formation of this mineral from the elements at the standard conditions was determined as −6196.6 ± 8.6 kJ mol⁻¹. The entropy of tooeleite, calculated from low-temperature heat capacity data measured by relaxation calorimetry, is 899.0 ± 10.8 J mol⁻¹ K⁻¹. The calculated standard Gibbs free energy of formation is −5396.3 ± 9.3 kJ mol⁻¹. The log K_sp value, calculated for the reaction Fe₆(AsO₃)₄(SO₄)(OH)₄·4H₂O + 16H⁺ = 6Fe³⁺ + 4H₃AsO₃ + SO₄²⁻ + 8H₂O, is −17.25 ± 1.80. Tooeleite has stability field only at very high activities of aqueous sulfate and arsenate. As such, it does not appear to be a good candidate for arsenic immobilization at polluted sites. An inspection of speciation diagrams shows that the predominance field of Fe³⁺ and As³⁺ overlap only at strongly basic conditions. The formation of tooeleite, therefore, requires strictly selective oxidation of Fe²⁺ to Fe³⁺ and, at the same time, firm conservation of the trivalent oxidation state of arsenic. Such conditions can be realized only by biological systems (microorganisms) which can selectively oxidize one redox-active element but leave the other ones untouched. Hence, tooeleite is the first example of an “obligatory” biomineral under the conditions prevailing at or near the Earth's surface because its formation under these conditions necessitates the action of microorganisms.     

Taipingite-(Ce), (Ce73+, Ca2)Σ9Mg(SiO4)3[SiO3(OH)]4F3, a new mineral from the Taipingzhen REE deposit,North Qinling Orogen,central China

A new cerite group mineral species, taipingite-(Ce), ideally (Ce₇³⁺, Ca₂)_Σ9Mg(SiO₄)₃[SiO₃(OH)]₄F₃, has been found in the Taipingzhen rare earth element (REE) deposit in the North Qinling Orogen (NQO), Central China. It forms subhedral grains (up to approximately 100 ​μm ​× ​200 ​μm) commonly intergrown with the REE mineral assemblages and is closely associated with allanite-(Ce), gatelite-(Ce), törnebohmite-(Ce), fluocerite-(Ce), fluocerite-(La), fluorite, bastnäsite-(Ce), parisite-(Ce) and calcite. Taipingite-(Ce) is light red to pinkish brown under a binocular microscope and pale brown to colorless in thin section, and it is translucent to transparent with a grayish-white streak and vitreous luster. This mineral is brittle with conchoidal fracture; has a Mohs hardness value of approximately 5½ and exhibits no cleavage twinning or parting. The calculated density is 4.900(5) g/cm³. Optically, taipingite-(Ce) is uniaxial (+), with ω ​= ​1.808(5), ε ​= ​1.812(7), c ​= ​ε, and a ​= ​b ​= ​ω. Furthermore, this mineral is insoluble in HCl, HNO₃ and H₂SO₄. Electron microprobe analysis demonstrated that the sample was relatively pure, yielding the empirical formula (with calculated H₂O): (Ce_4.02La_1.64Nd_1.49Pr_0.41Sm_0.10Gd_0.02Ho_0.02Tm_0.01Lu_0.02Y_0.03Ca_0.66Mg_0.05Th_0.01–0.51)_Σ9(Mg_0.75Fe_0.25³⁺)_Σ1(SiO₄)₃{[SiO₃(OH)]_3.98[PO₃(OH)]_0.02}_Σ4(F_1.81OH_1.17Cl_0.02)_Σ3. Taipingite-(Ce) is trigonal and exhibits space group symmetry R3c with unit cell parameters a ​= ​10.7246(3) Å, c ​= ​37.9528(14) Å, V ​= ​3780.39(20) ų and Z ​= ​6. The strongest eight lines in the X-ray diffraction pattern are [d in Å(I)(hkl)]: 4.518(50)(202), 3.455(95)(122), 3.297(85)(214), 3.098(35)(300), 2.941(100)(02,10), 2.683(65)(220), 1.945(40)(238) and 1.754(40)(30,18). The crystal structure has been refined to a R₁ factor of 0.025, calculated for the 2312 unique observed reflections (Fo ​≥ ​4σ). The mineral is named after its discovery locality and is characterized as the F-dominant analogue of cerite-(Ce).     

High-pressure structural studies of Li x La1/3NbO3 (x = 1/6, 1/3, 1/2, 2/3)

The high-pressure behavior of Li _x La_1/3NbO₃ (x = 1/6, 1/3, 1/2, 2/3) perovskites where Li cations were substituted for the existing vacancies was studied using synchrotron X-ray diffraction. It was shown that all these materials undergo irreversible pressure-induced amorphization around 14.5 GPa regardless of the Li concentration. The Li-inserted materials were found to exhibit a standard pressure response (bulk modulus pressure derivative B ₀′ ~4) when in the crystalline phase, whereas La_1/3NbO₃ shows a linear volume contraction versus pressure, i.e., B ₀′ ~(?1). These results suggest that the structural collapse is not a consequence of cation disorder resulting from the Nb atoms (B-site) migrating to the A-site vacancies. The observed pressure response can be understood by increased occupancy of the A-sites opposing the tilting of the NbO₆ octahedra. The pressure evolution of the Nb oxidation state is discussed.     

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.     

Potentiometric study of the stability of Eu3+ acetate complexes as a function of pressure (1–1000 bar) at 25°C

The stability of europium acetate complexes was examined potentiometrically at 25°C as a function of pressure in the range of 1–1000 bar. The measurements were carried out in an isothermal potentiometric cell with a liquid junction. The cell consisted of a pH glass electrode and an Ag, AgCl (3m KCl) reference electrode. The calibration of the cell on standard solutions has demonstrated that its electromotive force is independent of pressure. Based on pH measurements under various pressures in four acetate solutions with pH from 3 to 4.7 and containing 0.0142m Eu, we determined the standard partial mole volumes and the HKF parameters for the complexes Eu(Ac)²⁺ and Eu(Ac) ₂ ⁺ . The baric dependence of the Δ_f G ⁰ of the third complex, Eu(Ac) ₃ ⁰ , was evaluated from correlations. The stability of all three Eu acetate complexes decreased with pressure: as the pressure was increased from 1 to 1000 bar, the constants of formation of the complexes decreased by factors of 1.5–3 at 25°C and 2–6 at 170°C.     

Florencite-(Sm)—(Sm,Nd)Al3(PO4)2(OH)6: A new mineral species of the alunite-jarosite group from the subpolar urals

Florencite-(Sm), a new mineral species of the florencite subgroup, was found in association with xenotime-(Y) in quartz veins of the Maldynyrd Range of the Subpolar Urals as thin zones within rhombohedral crystals of florencite-(Ce) with faceting by { 01[`1]1}\{ 01\bar 11\} and { 10[`1]2}\{ 10\bar 12\} . The thickness of particular florencite-(Sm) zones is 0.01–0.1 mm, and the total thickness of a series of such zones is 1–3 mm. Florencite-(Sm) is colorless and pale pink or pale yellow with white streaks; its Mohs hardness is 5.5–6.0. Its measured and calculated densities are 3.70 and 3.743 g/cm³, respectively. The mineral is transparent, nonpleochroic, and uniaxial (positive), and ω = 1.704(2) and ɛ = 1.713(2). The electron beam’s fluorescence spectrum was 592 nm (intense green luminescence of Sm³⁺) and 558 nm (yellow luminescence of Nd³⁺). The chemical composition was as follows (microprobe, average of 2 WDS, wt %): 0.62 La₂O₃, 3.29 Ce₂O₃, 1.05 Pr₂O₃, 10.31 Nd₂O₃, 12.62 Sm₂O₃, 0.41 Eu₂O₃, 2.30 Gd₂O₃, 0.13 Dy₂O₃, 0.71 SrO, 0.35 CaO, 29.89 Al₂O₃, 26.14 P₂O₅, 0.85 SO₃, 0.09 SiO₂, 88.76 in total; 10.74 H₂O (meas.). The empirical formula based on 14 oxygen atoms is (Sm_0.38Nd_0.32Gd_0.07Ce_0.10Pr_0.03La_0.02Eu_0.01Sr_0.04Ca_0.03)1.0Al_3.04(P_1.91S_0.05Si_0.01)_1.97O₁₄H_5.92. The idealized formula is (Sm,Nd)Al₃(PO₄)₂(OH)₆. Mineral is trigonal, space group R3m, a = 6.972(4), c = 16.182(7) ?, V = 681.2 ?³, Z = 3. The XRD pattern is as follows: dln (I) (hkl): 2.925 (10) (113), 1.881 (6) (303), 2.161 (5) (107), 5.65 (4) (101), and 3.479 (4) (110). The IR spectrum: 466, 510, 621, 1036, 1105, 1223, 2957, and 3374 cm⁻¹.     

Structure and Mössbauer spectroscopy of barbosalite Fe2+Fe3+ 2 (PO4)2(OH)2 between 80 K and 300 K

Natural barbosalite Fe²⁺Fe³⁺ ₂ (PO₄)₂(OH)₂ from Bull Moose Mine, South Dakota, U.S.A., having ideal composition, was investigated with single crystal X-ray diffraction techniques, Mössbauer spectroscopy and SQUID magnetometry to redetermine crystal structure, valence state of iron and evolution of ⁵⁷Fe Mössbauer parameter and to propose the magnetic structure at low temperatures. At 298?K the title compound is monoclinic, space group P2₁/n, a _o ?= 7.3294(16)?Å, b _o ?=?7.4921(17)?Å, c _o ?=?7.4148 (18)?Å, β?=?118.43(3)°, Z?=?2. No crystallographic phase transition was observed between 298?K and 110?K. Slight discontinuities in the temperature dependence of lattice parameters and bond angles in the range between 150?K and 180?K are ascribed to the magnetic phase transition of the title compound. At 298?K the Mössbauer spectrum of the barbosalite shows two paramagnetic components, typical for Fe²⁺ and Fe³⁺ in octahedral coordination; the area ratio Fe³⁺/Fe²⁺ is exactly two, corresponding to the ideal value. Both the Fe²⁺ and the Fe³⁺ sublattice order magnetically below 173?K and exhibit a fully developed magnetic pattern at 160?K. The electric field gradient at the Fe²⁺ site is distorted from axial symmetry with the direction of the magnetic field nearly perpendicular to V_zz, the main component of the electric field gradient. The temperature dependent magnetic susceptibility exhibits strong antiferromagnetic ordering within the corner-sharing Fe³⁺-chains parallel to [101], whereas ferromagnetic coupling is assumed within the face-sharing [1?1?0] and [?1?1?0] Fe³⁺-Fe²⁺-Fe³⁺ trimer, connecting the Fe³⁺-chains to each other.     

Redefinition of Lemanskiite: New Mineralogical Data,Crystal Structure,and Revised Formula NaCaCu5(AsO4)4Cl · 3H2O

Geology of Ore Deposits - The crystal structure of lemanskiite is determined for the first time (R = 0.019) and the mineral is redefined. Its chemical formula, crystal system, space group and...     

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.     

Lammerite-β, Cu3(AsO4)2, a new mineral from fumaroles of the Great Fissure Tolbachik eruption, Kamchatka Peninsula, Russia

Lammerite-β, Cu₃(AsO₄)₂, occurs as a product of the post-eruption fumarole activity of the second cinder cone of the North breach of the Great Fissure Tolbachik eruption in 1975–1976, Kamchatka Peninsula, Russia. Sporadic light to dark green splinter-shaped grains are no larger than 0.15 mm in size. Cleavage is not observed. The mechanical admixture of finely dispersed hematite forms condensed brownish spots that are occasionally zonal relative to the contours of the lammerite-β grains. Associated minerals are euchlorine, piypite, alumoklyuchevskite, alarsite, and lammerite. Lammerite-β is brittle and transparent and has vitreous luster. The calculated density is 5.06 g/cm³. The mineral is not pleochroic, biaxial (+), α = 1.887(5), β = 1.936(5), γ = 2.01(1), 2V(calc.) = 80.9°; dispersion is strong, r < v. The new mineral is monoclinic, the space group is P2₁/c, a = 6.306(1), b = 8.643(1), c = 11.310(1) Å, β = 92.26(1)°, V = 615.9(1) ų, and Z = 4. Characteristic reflections in the X-ray powder diffraction pattern (I-d-hkl) are 100-2.83-004, 10-5.65-002, and 10-4.32-020. The chemical composition is as follows, wt %: 51.30 CuO, 0.32 ZnO, 49.12 As₂O₃, with a total of 100.74 wt %. The empirical and idealized formulas are Cu_3.00Zn_0.02As_1.99O₈ and Cu₃(AsO₄)₂, respectively.     

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。     

Thermodynamic properties of tellurite (β-TeO2), paratellurite (α-TeO2), TeO2 glass,and Te(IV) phases with stoichiometry M2Te3O8, MTe6O13, MTe2O5 (M2+ = Co,Cu, Mg,Mn, Ni,Zn)

Thermodynamic properties of several TeO₂ polymorphs and metal tellurites were measured by a combination of calorimetric techniques. The most stable TeO₂ polymorph is α-TeO₂, with its enthalpy of formation (Δ_fH^o) selected from literature data as ?322.0 ± 1.3 kJ·mol^?1. β-TeO₂ is metastable (in enthalpy) with respect to α-TeO₂ by +1.40 ± 0.07 kJ·mol^?1, TeO₂ glass by a larger amount of +14.09 ± 0.11 kJ·mol^?1. >200 experimental runs and post-synthesis treatments were performed in order to produce phase-pure samples of Co, Cu, Mg, Mn, Ni, Zn tellurites. The results of the hydrothermal and solid-state syntheses are described in detail and the products were characterized by powder X-ray diffraction. The standard thermodynamic data for the Te(IV) phases are (standard enthalpy of formation from the elements, Δ_fH^o in kJ·mol^?1, standard third-law entropy S^o in J·mol^?1·K^?1): Co₂Te₃O₈: Δ_fH^o = ?1514.2 ± 6.0, S^o = 319.2 ± 2.2; CoTe₆O₁₃: Δ_fH^o = ?2212.5 ± 8.1, S^o = 471.7 ± 3.3; MgTe₆O₁₃: Δ_fH^o = ?2525.8 ± 7.9, S^o = 509.2 ± 3.6; Ni₂Te₃O₈: Δ_fH^o not measured, S^o = 293.3 ± 2.1; NiTe₆O₁₃: Δ_fH^o = ?2198.7 ± 8.2, S^o = 466.5 (estimated); CuTe₂O₅: Δ_fH^o = ?820.2 ± 3.3, S^o = 187.2 ± 1.3; Zn₂Te₃O₈: Δ_fH^o = ?1722.5 ± 4.0, S^o = 299.3 ± 2.1. The solubility calculations show that the Te(IV) concentration in an aqueous phase, needed to produce such phases, must be at least 3–5 orders of magnitude higher than the natural Te background concentrations. The occurrence of these minerals, as expected, are restricted to hotspots of Te concentrations. In order to produce more reliable phase diagrams, more work needs to be done on the thermodynamics of potential competing phases in these systems, including Te(VI) phases.     

Influence of hydroxybenzoic acids on the adsorption of Eu(III) onto α,γ-Al2O3 particles in mildly acidic conditions: A macroscopic and spectroscopic study

The influence of hydroxybenzoic acids (HAH_n), namely p-hydroxybenzoic acid (4-hydroxybenzoic acid, HPhbH) and protocatechuic acid (3,4-dihydroxybenzoic acid, HProtoH₂), on the adsorption of europium(III) onto α,γ-Al₂O₃ particles is studied as a function of acid concentration. After measuring the adsorption edge of the Eu(III)/α,γ-Al₂O₃ binary system, and using the previously studied binary component system Eu(III)/HAH_n—Moreau et al. (2015) Inorg. Chim. Acta 432, 81—, and HAH_n/α,γ-Al₂O₃—Moreau et al. (2013) Colloids Surf. A 435, 97—, it is evidenced that HPhbH does not enhance Eu(III) adsorption onto α,γ-Al₂O₃ in the Eu(III)/HPhbH/α,γ-Al₂O₃ ternary system. Conversely, HProtoH₂ enhances Eu(III) adsorption onto α,γ-Al₂O₃ in the Eu(III)/HProtoH₂/α,γ-Al₂O₃ ternary system. Adsorption of the acids are also found higher in the Eu(III)/acid/α,γ-Al₂O₃ ternary systems as compared with the corresponding binary systems assessing synergetic effects. For high HPhbH concentrations, a ternary surface species involving ≡AlOH surface sites, Eu(III), and PhbH^– is evidenced by time-resolved luminescence spectroscopy (TRLS). However, in the Eu(III)/HProtoH₂/α,γ-Al₂O₃ ternary system, chemical environment of Eu(III) is found to be very close to that in the Eu(III)/HProtoH₂ binary system. Ternary surface species could not be evidenced in the Eu(III)/HProtoH₂/α,γ-Al₂O₃ ternary system with TRLS because of the very short decay time of Eu(III) in the presence of protocatechuic acid.     

Günterblassite, (K,Ca)3 − x Fe[(Si,Al)13O25(OH,O)4] · 7H2O, a new mineral: the first phyllosilicate with triple tetrahedral layer

A new mineral, günterblassite, has been found in the basaltic quarry at Mount Rother Kopf near Gerolstein, Rheinland-Pfalz, Germany as a constituent of the late assemblage of nepheline, leucite, augite, phlogopite, åkermanite, magnetite, perovskite, a lamprophyllite-group mineral, götzenite, chabazite-K, chabazite-Ca, phillipsite-K, and calcite. Günterblassite occurs as colorless lamellar crystals up to 0.2 × 1 × 1.5 mm in size and their clusters. The mineral is brittle, with perfect cleavage parallel to (001) and less perfect cleavage parallel to (100) and (010). The Mohs hardness is 4. The calculated and measured density is 2.17 and 2.18(1) g/cm³, respectively. The IR spectrum is given. The new mineral is optically biaxial and positive as follows: α = 1.488(2), β = 1.490(2), γ = 1.493(2), 2V _meas = 80(5)°. The chemical composition (electron microprobe, average of seven point analyses, H₂O is determined by gas chromatography, wt %) is as follows: 0.40 Na₂O, 5.18 K₂O, 0.58 MgO, 3.58 CaO, 4.08 BaO, 3.06 FeO, 13.98 Al₂O₃, 52.94 SiO₂, 15.2 H₂O, and the total is 98.99. The empirical formula is Na_0.15K_1.24Ba_0.30Ca_0.72Mg_0.16F _0.48 ²⁺ [Si_9.91Al_3.09O_25.25(OH)_3.75] · 7.29H₂O. The crystal structure has been determined from a single crystal, R = 0.049. Günterblassite is orthorhombic, space group Pnm2₁; the unit-cell dimensions are a = 6.528(1), b = 6.970(1), c = 37.216(5) Å, V = 1693.3(4) ų, Z = 2. Günterblassite is a member of a new structural type; its structure is based on three-layer block [Si₁₃O₂₅(OH,O)₄]. The strong reflections in the X-ray powder diffraction pattern [d Å (I, %) are as follows: 6.532 (100), 6.263 (67), 3.244 (49), 3.062 (91), 2.996 (66), 2.955 (63), and 2.763 (60). The mineral was named in honor of Günter Blass (born in 1943), a well-known amateur mineralogist and specialist in electron microprobe and X-ray diffraction. The type specimen of günterblassite is deposited in the collections of the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, Russia, with the registration number 4107/1.     

U–Pb and Re–Os isotopic systematics and zircon Ce4 +/Ce3 + ratios in the Shiyaogou Mo deposit in eastern Qinling,central China: Insights into the oxidation state of granitoids and Mo (Au) mineralization

The newly-discovered Shiyaogou molybdenum deposit is located in the eastern Qinling metallogenic belt in central China. The deposit contains at least 152,000 t of Mo metal and bears typical porphyry-type features in terms of its concentric alteration zonation, quartz vein-hosted Mo mineralization, veining sequence and the spatial association with concealed granite porphyries. Re–Os isotope analyses of molybdenite from the deposit yield an ore-forming age of 132.3 ± 2.8 Ma. LA-ICP-MS U–Pb zircon dating of ore-related porphyries yields crystallization ages from 135 Ma to 132 Ma, indicating a temporal link between granitic magmatism and Mo mineralization. A population of captured magmatic zircons indicates another pulse of magmatism at ~ 143 Ma. A barren granite intrusion near the deposit gives a zircon U–Pb age of 148.1 ± 1.1 Ma. These magmatic activities were concurrent with the emplacement of the nearby Heyu granitic batholith, a largely ore-barren intrusive complex formed from ~ 148 Ma to ~ 127 Ma. Zircon Ce^4 +/Ce^3 + ratios of ore-related porphyries are obviously higher than those of contemporaneous barren granitoids, implying an affinity between Mo mineralization and highly oxidized magmas. Moreover, zircons from these granitoids overall have decreasing Ce^4 +/Ce^3 + ratios from 148 Ma to 132 Ma, reflecting decreasing oxygen fugacities during magma evolution. Available geological, radiometric and stable isotopic evidence suggests that the decrease of magma oxygen fugacity was probably associated with an increase of mantle contribution to granitic magmatism and metallogenesis, which probably gave rise to successive mineralization of Mo and Au in the eastern Qinling. The intense magmatic–metallogenic events in the eastern Qinling during Late Jurassic to Early Cretaceous times are interpreted as a response to the large-scale lithosphere thinning and subsequent asthenosphere upwelling beneath the eastern part of the North China Craton.     

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).     

Late Pleistocene (MIS 3–4) climate inferred from micromammal communities and δO of rodents from Les Pradelles,France

The middle Paleolithic stratigraphic sequence of Les Pradelles (Charente, France) spans from the end of Marine Isotope Stage (MIS) 4 until the middle of MIS 3. Micromammal remains are present in all the stratigraphic levels, offering a rare opportunity to address the questions of both environmental and climatic fluctuations throughout this period. Climate modes were studied through the taphonomy, biodiversity and oxygen isotope compositions of phosphate (δ¹⁸O_p) from 66 samples of rodent tooth enamel. The δ¹⁸O_p values from the lower sedimentary levels provide summer mean air temperatures of 19 ± 2°C (level 2/1) and of 16 ± 2°C (levels 2A, 2B and 4A). Within the middle of sequence (level 4B), a paleobiodiversity change can be identified with an increase of Dicrostonyx torquatus, which is associated with the largest amplitude in δ¹⁸O_p values and the highest maximal δ¹⁸O_p values. At the top of the sequence (level 5-2), a biodiversity change is observed with the increase of Microtus arvalis, but without any change in δ¹⁸O_p values. The association of cold rodent species with unexpected high and large amplitudes in the δ¹⁸O_p values of their teeth, possibly indicative of aridity, suggests their deposition during a Heinrich event.     

Solubility of Ca6[Al(OH)6]2(CrO4)3·26H2O,the chromate analog of ettringite; 5–75°C

Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O, the chromate analog of the sulfate mineral ettringite, was synthesized and characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analyses, energy dispersive X-ray spectrometry, and bulk chemical analyses. The solubility of the synthesized solid was measured in a series of dissolution and precipitation experiments conducted at 5–75°C and at initial pH values between 10.5 and 12.5. The ion activity product (IAP) for the reaction Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O⇌6Ca²⁺+2Al(OH)⁻₄+3CrO²⁻₄+4OH⁻+26H₂O varies with pH unless a CaCrO_4(aq) complex is included in the speciation model. The log K for the formation of this complex by the reaction Ca²⁺+CrO²⁻₄=CaCrO_4(aq) was obtained by minimizing the variance in the IAP for Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O. There is no significant trend in the formation constant with temperature and the average log K is 2.77±0.16 over the temperature range 5–75°C. The log solubility product (log K_SP) of Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O at 25°C is −41.46±0.30. The temperature dependence of the log K_SP is log K_SP=A−B/T+D log(T) where A=498.94±48.99, B=27,499±2257, and D=−181.11±16.74. The values of ΔG⁰_r,298 and ΔH⁰_r,298 for the dissolution reaction are 236.6±3.9 and 77.5±2.4 kJ mol⁻¹. the values of ΔC⁰_P,r,298 and ΔS⁰_r,298 are −1506±140 and −534±83 J mol⁻¹ K⁻¹. Using these values and published standard state partial molal quantities for constituent ions, ΔG⁰_f,298=−15,131±19 kJ mol⁻¹, ΔH⁰_f,298=−17,330±8.6 kJ mol⁻¹, ΔS⁰₂₉₈=2.19±0.10 kJ mol⁻¹ K⁻¹, and ΔC⁰_Pf,298=2.12±0.53 kJ mol⁻¹ K⁻¹, were calculated.