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     

Orschallite,Ca3(SO3)2 · SO4 · 12H2O,a new calcium-sulfite-sulfate-hydrate mineral

Summary The new mineral orschallite, Ca₃(SO₃)₂SO₄ · 12H₂O, was found at the Hannebacher Ley near Hannebach, Eifel, Germany. Crystal structure analysis of the mineral, chemical analysis and water determination on synthetic material gave the composition Ca₃(SO₃)₂SO₄ · 12H₂O. The mineral crystallizes in space group with a = 11.350(1), c = 28.321(2) Å, V = 3159.7 ų, Z = 6, D_c = 1.87 Mg/m³, D_m = 1.90(3) Mg/m³. It is uniaxial positive with the optical constants = 1.4941, = 1.4960(4). The strongest lines in the powder pattern are (d-value (Å), I, hkl) 5.73, 100, 1 0 4/8.11, 80, 0 1 2/2.69, 80, 3 0 6/3.63, 60, 1 1 6/3.28, 40, 3 0 0. Refinement of the crystal structure led to a weighted residual of R_w = 0.043 for 600 observed reflections with I > 2(I) and 52 variable parameters.

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Orschallit, Ca₃(SO₃)₂SO₄ · 12H₂O, ein neues Kalzium-Sulfat-Sulfat-Hydrat-Mineral

Zusammenfassung Das neue Mineral Orschallit, Ca₃(SO₃)₂SO₄ · 12H₂O, wurde in der Hannebacher Ley bei Hannebach, Eifel, Deutschland gefunden. Eine Analyse der Kristallstruktur an einem Einkristall des natürlichen Materials, chemische Analyse und Wasserbestimmung an synthetischem Material ergaben die Zusammensetzung Ca₃(SO₃)₂SO₄ · 12H₂O. Das Mineral kristallisiert in der Raumgruppe mit a = 11.350(1), c = 28.321(2) Å, V = 3159.7 ų, Z = 6, D_c = 1.87 Mg/m³, D_m = 1.90(3) Mg/m³. Es ist optisch einachsig mit den optischen Konstanten = 1.4941, = 1.4960(4). Die stärksten Linien des Pulver-diagramms liegen bei (d-Wert (Å), I, hkl) 5.73, 100, 1 0 4/8.11, 80, 0 1 2/2.69, 80, 3 0 6/3.63, 60; 1 1 6/3.28, 40, 3 0 0. Die Verfeinerung der Kristallstruktur ergab einen gewichteten Residualwert R_w = 0.043 für 600 beobachtete Reflexe mit I > 2(I) und 52 variable Parameter.

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With 5 Figures     

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     

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.     

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.     

Shear modulus, heat capacity, viscosity and structural relaxation time of Na2O–Al2O3–SiO2 and Na2O–Fe2O3–Al2O3–SiO2 melts

The configurational heat capacity, shear modulus and shear viscosity of a series of Na₂O–Fe₂O₃–Al₂O₃–SiO₂ melts have been determined as a function of composition. A change in composition dependence of each of the physical properties is observed as Na₂O/(Na₂O + Al₂O₃) is decreased, and the peralkaline melts become peraluminous and a new charge-balanced Al-structure appears in the melts. Of special interest are the frequency dependent (1 mHz–1 Hz) measurements of the shear modulus. These forced oscillation measurements determine the lifetimes of Si–O bonds and Na–O bonds in the melt. The lifetime of the Al–O bonds could not, however, be resolved from the mechanical spectrum. Therefore, it appears that the lifetime of Al–O bonds in these melts is similar to that of Si–O bonds with the Al–O relaxation peak being subsumed by the Si–O relaxation peak. The appearance of a new Al-structure in the peraluminous melts also cannot be resolved from the mechanical spectra, although a change in elastic shear modulus is determined as a function of composition. The structural shear-relaxation time of some of these melts is not that which is predicted by the Maxwell equation, but up to 1.5 orders of magnitude faster. Although the configurational heat capacity, density and shear modulus of the melts show a change in trend as a function of composition at the boundary between peralkaline and peraluminous, the deviation in relaxation time from the Maxwell equation occurs in the peralkaline regime. The measured relaxation times for both the very peralkaline melts and the peraluminous melts are identical with the calculated Maxwell relaxation time. As the Maxwell equation was created to describe the timescale of flow of a mono-structure material, a deviation from the prediction would indicate that the structure of the melt is too complex to be described by this simple flow equation. One possibility is that Al-rich channels form and then disappear with decreasing Si/Al, and that the flow is dominated by the lifetime of Si–O bonds in the Al-poor peralkaline melts, and by the lifetime of Al–O bonds in the relatively Si-poor peralkaline and peraluminous melts with a complex flow mechanism occurring in the mid-compositions. This anomalous deviation from the calculated relaxation time appears to be independent of the change in structure expected to occur at the peralkaline/peraluminous boundary due to the lack of charge-balancing cations for the Al-tetrahedra.     

(2)PALEOBOTANY (3)PALEOZOOLOGY

971349 Che;19 Jie(China Universityseienees,Beijing)The MammaljanShowjng ClimatieF盆uetuat应on—ExamPle of the Early Pleistoceneof Ge。FaunaS AS anMam-malian Faunas from Zhoukoudian,Beijing,China(ESI矛,ISSN 1 005一2321,CN 11一3370/P,4(2),1997,p·275一279,1 graph,1 table,10 ref) By analyses of the four local marnmalianfaunas from Zhoukoudian,Beijing,the EarlyPleistoeene elimatie and eeologieal environ-CN 11一1 905/Q1 53,1 graph,1735(2).1997,P.145一mental ehangespaper.One of1 .90M…     

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.     

Batagayite,CaZn2(Zn,Cu)6(PO4)4(PO3OH)3·12H2O,a new phosphate mineral from Këster tin deposit (Yakutia,Russia): occurrence and crystal structure

Mineralogy and Petrology - Batagayite, CaZn2(Zn,Cu)6(PO4)4(PO3OH)3·12H2O, is a new secondary phosphate mineral from the Këster deposit, Arga-Ynnykh-Khai massif, NE Yakutia, Russia. It is...     

Sergeysmirnovite,MgZn2(PO4)2 · 4H2O,a New Mineral from the Kester Deposit (Sakha-Yakutia,Russia)

Doklady Earth Sciences - Sergeysmirnovite, MgZn2(PO4)2 · 4H2O, is a new mineral from the oxidation zone of the Kester mineral deposit, Sakha-Yakutia, Russia. This mineral forms...     

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.     

Hillesheimite, (K,Ca,□)2(Mg,Fe,Ca,□)2[(Si,Al)13O23(OH)6](OH) · 8H2O, a new phyllosilicate mineral of the Günterblassite group

A new mineral, hillesheimite, has been found in the Graulai basaltic quarry, near the town of Hillesheim, the Eifel Mountains, Rhineland-Palatinate (Rheinland-Pfalz), Germany. It occurs in the late assemblage comprising nepheline, augite, fluorapatite, magnetite, perovskite, priderite, götzenite, lamprophyllite-group minerals, and åkermanite. Colorless flattened crystals of hillesheimite reaching 0.2 × 1 × 1.5 mm in size and aggregates of the crystals occur in miarolitic cavities in alkali basalt. The mineral is brittle, with Mohs’ hard-ness 4. Cleavage is perfect parallel to (010) and distinct on (100) and (001). D _calc = 2.174 g/cm³, D _meas = 2.16(1) g/cm³. IR spectrum is given. Hillesheimite is biaxial (?), α = 1.496(2), β = 1.498(2), γ = 1.499(2), 2V _meas = 80°. The chemical composition (electron microprobe, mean of 4 point analyses, H₂O determined from structural data, wt %) is as follows: 0.24 Na₂O, 4.15 K₂O, 2.14 MgO, 2.90 CaO, 2.20 BaO, 2.41 FeO, 15.54 Al₂O₃, 52.94 SiO₂, 19.14 H₂O, total is 101.65. The empirical formula is: K_0.96Na_0.08Ba_0.16Ca_0.56Mg_0.58Fe _0.37 ²⁺ [Si_9.62Al_3.32O₂₃(OH)₆][(OH)_0.82(H₂O)_0.18] · 8H₂O. The crystal structure has been determined from X-ray single-crystal diffraction data, R = 0.1735. Hillesheimite is orthorhombic, space group Pmmn, the unit-cell dimensions are: a = 6.979(11), b = 37.1815(18), c = 6.5296(15) Å; V=1694(3) ų, Z = 2. The crystal structure is based on the block [(Si,Al)₁₃O₂₅(OH)₄] consisting of three single tetrahedral layers linked via common vertices and is topologically identical to the triple layers in günterblassite and umbrianite. The strong reflections [d Å (I %)] in the X-ray powder diffraction pattern are: 6.857(58), 6.545(100), 6.284(53), 4.787(96), 4.499(59), 3.065(86), 2.958(62), 2.767(62). The mineral was named after its type locality. Type specimens are deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, registration number 4174/1.     

A study on the effects of drying conditions on the stability of NaNd(CO3)2·6H2O and NaEu(CO3)2·6H2O

The effect of different drying conditions on the stability of NaNd(CO₃)·6H₂O and NaEu(CO₃)·6H₂O and the identity of the decomposition product have been investigated. The rate of decomposition and the nature of the altered phases are dependant on the drying conditions used. When the phases are oven dried at 120 °C, the decomposition is immediate and the phase completely alters to Nd₂(CO₃)₃ or Eu₂(CO₃)₃ respectively. Under less severe drying conditions, the Na rare earth carbonate phases alter to Nd₂(CO₃)₃·8H₂O and Eu₂(CO₃)₃·8H₂O over a period of 24–48 h, but they can be kept indefinitely in a water saturated environment. The implications for using Nd and Eu as actinide analogues are discussed.     

Description and crystal structure of albrechtschraufite, MgCa4F2[UO2(CO3)3]2⋅17-18H2O

Albrechtschraufite, MgCa₄F₂[UO₂(CO₃)₃]₂?17-18H₂O, triclinic, space group Pī, a?=?13.569(2), b?=?13.419(2), c?=?11.622(2) Å, α?=?115.82(1), β?=?107.61(1), γ?=?92.84(1)° (structural unit cell, not reduced), V?=?1774.6(5) ų, Z?=?2, D _c?=?2.69 g/cm³ (for 17.5 H₂O), is a mineral that was found in small amounts with schröckingerite, NaCa₃F[UO₂(CO₃)₃](SO₄)?10H₂O, on a museum specimen of uranium ore from Joachimsthal (Jáchymov), Czech Republic. The mineral forms small grain-like subhedral crystals (≤ 0.2 mm) that resemble in appearance liebigite, Ca₂[UO₂(CO₃)₃]??~?11H₂O. Colour pale yellow-green, luster vitreous, transparent, pale bluish green fluorescence under ultraviolet light. Optical data: Biaxial negative, nX?=?1.511(2), nY?=?1.550(2), nZ?=?1.566(2), 2?V?=?65(1)° (λ?=?589 nm), r < v weak. After qualitative tests had shown the presence of Ca, U, Mg, CO₂ and H₂O, the chemical formula was determined by a crystal structure analysis based on X-ray four-circle diffractometer data. The structure was later on refined with data from a CCD diffractometer to R1?=?0.0206 and wR2?=?0.0429 for 9,236 independent observed reflections. The crystal structure contains two independent [UO₂(CO₃)₃]^4? anions of which one is bonded to two Mg and six Ca while the second is bonded to only one Mg and three Ca. Magnesium forms a MgF₂(O_carbonate)₃(H₂O) octahedron that is linked via the F atoms with three Ca atoms so as to provide each F atom with a flat pyramidal coordination by one Mg and two Ca. Calcium is 7- and 8-coordinate forming CaFO₆, CaF₂O₂(H₂O)₄, CaFO₃(H₂O)₄ and CaO₂(H₂O)₆ coordination polyhedra. The crystal structure is built up from MgCa₃F₂[UO₂(CO₃)₃]?8H₂O layers parallel to (001) which are linked by Ca[UO₂(CO₃)₃]?5H₂O moieties into a framework of the composition MgCa₄F₂[UO₂(CO₃)₃]?13H₂O. Five additional water molecules are located in voids of the framework and show large displacement parameters. One of the water positions is partly vacant, leading to a total water content of 17-18H₂O per formula unit. The MgCa₃F₂[UO₂(CO₃)₃]?8H₂O layers are pseudosymmetric according to plane group symmetry cmm. The remaining constituents do not sustain this pseudosymmetry and make the entire structure truly triclinic. A characteristic paddle-wheel motif Ca[UO₂(CO₃)₃]₄Ca relates the structure of albrechtschraufite partly to that of andersonite and two synthetic alkali calcium uranyl tricarbonates.     

一种钨的新矿物——蓟县矿Pb(W,Fe~(3+))_2(O,OH)_7

该矿物为一具烧绿石型结构,主要含WO_3、PbO、Fe_2O_3、H_2O~+的复杂氧化物新矿物。发现于河北省蓟县沿河钨矿床中,为氧化带的次生矿物。根据产地命名为蓟县矿(Jixianite)。该矿物的标本存放在国家地质总局地质博物馆。     

Thermodynamics of (Fe2+, Mn2+, Mg, Ca)3− Al2Si3O12 garnet: a review and analysis

Summary The thermodynamic properties of garnets in the system (Fe²⁺, Mn²⁺, Mg, Ca)₃A1₂Si₃O₁₂ are reviewed. The thermodynamic properties of the three end-member garnets pyrope, almandine and grossular, including their volume, enthalpy of formation, entropy, compressibility and thermal expansion have been well determined. For spessartine enthalpy of formation and heat capacity at low temperatures are needed. Pyrope's unusual behavior in some of its properties is probably related to the presence of the small, light Mg cation, which has a large anisotropic thermal vibration. The thermodynamic mixing properties of the six binaries are also discussed. Good volume of mixing data exist now for all of the binaries, but much work is still required to determine the enthalpies and third-law vibrational entropies of mixing. It is shown that the magnitude of the positive deviations in the volumes of mixing is related to the volume difference between the two end-member components. It is probable that excess entropies, if present, originate at low temperatures below 200 K. Recent²⁹Si NMR experiments have demonstrated the presence of short-range ordering (SRO) of Ca and Mg in pyrope-grossular solid solutions. Short-range order will have to be considered in new models describing the entropies of mixing. Its possible presence in all garnet solid solutions needs to be examined. The mixing properties of pyrope-grossular garnets, which are the best known for any garnet binary, can, in part, be described by the Quasi-Chemical approximation, which gives insight into the microscopic interactions which determine the macroscopic thermodynamic mixing properties. Microscopic properties are best investigated by spectroscopic and computational approaches. Hard mode IR measurements on binary solid solutions show that the range of local microscopic structural distortion is reflected in the macroscopic volumes of mixing. The nature of The contents of this contribution was presented at the IMA Meeting in Toronto in August, 1998. It precedes issues of Mineralogy and Petrology containing thematic sets of IMApapers strain tiields and site relaxation needs to be studied in order to obtain a better understanding of the solid-solution process and energetics in garnet. Critical areas for future experimentation are also addressed.[/p]

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Eine kritische Zusammenstellung und Analyse der thermodynamischen Daten der (Fe²⁺, Mn²⁺, Mg, Ca)₃Al₂Si₃O₁₂ granate

Zusammenfassung In dieser Studie werden die thermodynamischen Eigenschaften der Granate im System (Fe²⁺,Mn²⁺, Mg, Ca)₃Al₂Si₃O₁₂ kritisch zusammengestellt. Die thermodynamischen Eigenschaften der drei Endglied-Granate Pyrop, Almandin und Grossular, einschließlich ihrer Volumina, Bildungswärmen, Entropien, Kompressibilitäten und thermischen Ausdehnungen wurden bereits hinreichend gut bestimmt. Dagegen müssen die Bildungswärme und Tieftemperatur-Wärmekapazität von Spessartin noch gemessen werden. Die Eigenschaften des Pyrops sind wahrscheinlich mit den großen anisotropen Schwingungen des kleinen, leichten Mg-Kations verbunden. Die thermodynamischen Mischungseigenschaften der sechs binären Mischkristallreihen werden ebenfalls diskutiert. Während die Mischungs-Volumendaten der binären Mischreihen gut bekannt sind, müssen ihre Mischungs-Enthalpien und Standard-Mischungsentropien noch ermittelt werden. Es wurde gezeigt, daß die Größe der positiven Exzeß-Volumina mit dem Volumen-Unterschied der zwei Endglied-Komponenten der jeweiligen Mischreihe verknüpft ist. Es ist wahrscheinlich, daß Exzeß-Entropien, wenn vorhanden, erst bei Tieftemperaturen unter 200 K auftreten. Neue²⁹Si NMR-Experimente belegen, daß in Pyrop-Grossular-Mischkristallen Nahordnung von Mg und Ca vorliegt. Der Effekt der Nahordnung muß in künftigen thermodynamischen Modellen berücksichtigt werden. Hieraus ergibt sich die Notwendigkeit, alle Granat-Mischreihen auf mögliche Nahordnung hin zu untersuchen. Die Mischungseigenschaften der Pyrop-Grossular-Mischreihe, die von sämtlichen Granat-Mischreihen am besten bestimmt wurden, können teilweise mit dem Quasi-Chemical-Model beschrieben werden. Dieses Modell ermöglicht die Beschreibung der mikroskopischen Wechselwirkungen, die die makroskopischen thermodynamischen Eigenschaften bestimmen. Mikroskopische Eigenschaften werden am besten mit spektroskopischen Messungen und theoretischen Berechnungen untersucht. Hard-mode IR-Spektroskopie-Messungen an binären Mischreihen zeigen, daß die lokalen mikroskopischen strukturellen Verzerrungen in den makroskopischen Mischungs-Volumina widergespiegelt werden. Die Art der Spannungsfelder und Platz-Relaxationen muß detaillierter untersucht werden, um ein besseres Verständnis des Mischkristall-Bildungsprozsses und der Energetik der Granate zu erreichen. Darüber hinaus werden wichtige künftige Forschungsgebiete diskutiert.

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With 11 Figures     

The crystal structure of galgenbergite-(Ce), CaCe2(CO3)4∙H2O

Galgenbergite-(Ce) from the type locality, the railroad tunnel Galgenberg between Leoben and St. Michael, Styria, Austria, was investigated. There it occurs in small fissures of an albite-chlorite schist as very thin tabular crystals building rosette-shaped aggregates associated with siderite, ancylite-(Ce), pyrite and calcite. Electron microprobe analyses gave CaO 9.49, Ce₂O₃ 28.95, La₂O₃ 11.70, Nd₂O₃ 11.86, Pr₂O₃ 3.48, CO₂ 30.00, H₂O 3.07, total 98.55 wt.%. CO₂ and H₂O calculated by stoichiometry. The empirical formula (based on Ca + REE ∑3.0) is $ \mathrm{C}{{\mathrm{a}}_{1.00 }}{{\left( {\mathrm{C}{{\mathrm{e}}_{1.04 }}\mathrm{L}{{\mathrm{a}}_{0.42 }}\mathrm{N}{{\mathrm{d}}_{0.42 }}\mathrm{P}{{\mathrm{r}}_{0.12 }}} \right)}_{2.00 }}{{\left( {\mathrm{C}{{\mathrm{O}}_3}} \right)}_4}\cdot {{\mathrm{H}}_2}\mathrm{O} $ , and the simplified formula is $ \mathrm{CaC}{{\mathrm{e}}_2}{{\left( {\mathrm{C}{{\mathrm{O}}_3}} \right)}_4}\cdot {{\mathrm{H}}_2}\mathrm{O} $ . According to X-ray single crystal diffraction galgenbergite-(Ce) is triclinic, space group $ P\overline{1},a=6.3916(5) $ , b?=?6.4005(4), c?=?12.3898(9) Å, α?=?100.884(4), β?=?96.525(4), γ?=?100.492(4)°, V?=?483.64(6) ų, Z?=?2. The eight strongest lines in the powder X-ray diffraction pattern are [d _calc in Å/(I)/hkl]: 5.052/(100)/011; 3.011/(70)/0-22; 3.006/(66)/004; 5.899/(59)/-101; 3.900/(51)/1-12; 3.125/(46)/-201; 2.526/(42)/022; 4.694/(38)/-102. The infrared absorption spectrum reveals H₂O (OH-stretching mode at 3,489 cm^?1, HOH bending mode at 1,607 cm^?1) and indicates the presence of distinctly non-equivalent CO₃-groups by double and quadruple peaks of their ν1, ν2, ν3 and ν4 modes. The crystal structure of galgenbergite-(Ce) was refined with X-ray single crystal data to R1?=?0.019 for 2,448 unique reflections (I?>?2σ(I)) and 193 parameters. The three cation sites of the structure Ca(1), Ce(2) and Ce(3) have a modest mixed site occupation by Ca and small amount of REE (Ce, La, Pr, Nd) and vice versa. The structure is based on double layers parallel to (001), which are composed of Ca(1)Ce(2)(CO₃)₂ single layers with an ordered chessboard like arrangement of Ca and Ce, and with a roof tile-like stacking of the CO₃ groups. Perpendicular to (001) the double layers are connected to a triclinic framework structure with good cleavage parallel to (001) by a differently organized and more open part of the structure formed by Ce(3)(CO₃)₂(H₂O). Based on the topology of the CaCe(CO₃)₂ single layer in galgenbergite-(Ce), structural relationships to rutherfordine, to aragonite and ancylite type minerals, and to lanthanite are outlined.     

Mössbauer spectroscopic and x-ray powder diffraction studies of synthetic micas on the join annite KFe3AlSi3O10(OH)2-phlogopite KMg3AlSi3O10(OH)2

Micas of the composition K(Fe_3–x Mg _x )AlSi₃ O₁₀(OH)₂ (x=0.6, 1.2, 1.8, 2.4 and 3.0, corresponding to ann₈₀phl₂₀, ann₆₀phl₄₀, ann₄₀phl₆₀, ann₂₀phl₈₀ and ann₀phl₁₀₀) were synthesized hydrothermally under controlled oxygen fugacity conditions. Lattice parameters a ₀ and b ₀ show a distinct linear decrease with increasing Mg content. With increasing ferric iron content a deviation from this linear trend is observed especially within iron rich samples. The tetrahedral rotation angle increases smoothly from 0° in annite to 9.1° in phlogopite. Mössbauer spectra show Fe²⁺ and Fe³⁺ on the octahedral M1 and M2 sites and partially also Fe³⁺ on the tetrahedral site. There is a smooth increase of the quadrupole splitting on both the M1 and the M2 site going from annite to phlogopite, probably due to changes in the lattice contribution to the electric field gradient, assuming a positive correlation between quadrupole splitting and distortion. Fe³⁺ contents, as determined by Mössbauer spectroscopy, versus oxygen fugacity shows that, depending on the composition of the micas, minimum amounts of Fe³⁺ are present. For ann₈₀phl₂₀ this minimum amount of Fe³⁺ is about 8% decreasing to about 1–2% Fe³⁺ for ann₂₀phl₈₀.The molar volume of each solid solution member has been estimated from the determined relations of the molar volume versus % Fe³⁺ contents, extrapolated back to 0% Fe³⁺. Plotting these volumes as a function of X_phl shows that negative excess volume occur in the annitephlogopite join, with the maximum deviation from ideality around X _phl=0.3. Margules volume parameters have been constrained as: Wv, AnnPhl=0.018±0.016 J/(bar.mol) and Wv, PhlAnn=-0.391±0.025 J(bar.mol) (three site basis).     

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。