Synthesis,lattice constants and OH-valence vibrations of an orthorhombic amphibole with excess OH in the system Li2O-MgO-SiO2-H2O

Orthorhombic amphiboles with excess OH, which can be schematically deduced from anthophyllite by the combined substitutions Mg²⁺ + O^2–Li⁺+OH^– and Mg²⁺2 Li⁺, were synthesized at 750–875° C/1 kbar in the system Li₂O-MgO-SiO₂-H₂O. Their phase relations are presented for 800° C/1 kbar . An amphibole with the analytical composition 2.70 wt% Li₂O, 31.1 wt% MgO, 63.0 wt% SiO₂, and 3.29 wt% H₂O has lattice constants a ₀ 18.588 (11), b ₀ 17.966 (10), c ₀ 5.262 (3) Å, V ₀ 1,757.2 (1.5) ų (referred to Space Group Pnma). The OH-valence vibrational spectrum of this amphibole showed v _OH bands at 3,667, 3,708, and 3,725 (shoulder) cm^–1, which are ascribed to OH in the configurations (MgMgMg)-OH, (MgMgMg)-OH-Li (Li in the A-site) of the pseudotrigonal (M1M1M3)-OH arrangement in the amphibole structure, and to Si-OH, respectively. No explanation can at present be offered for an additional shoulder at 3,695 cm^–1. The proposed structural formula is (Li_{0.27 0.73})(Li_1.11 Mg_0.89)· (Mg₅)(Si_8.01O_21.20(OH)_0.80)(OH)_2.00.     

Synthesis and stability of deerite,Fe 12 2+ Fe 6 3+ [Si12O40](OH)10, and Fe3+⇋Al3+ substitutions at 15–28 kb

Deerite, Fe ₁₂ ²⁺ Fe ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀, thus far known from ten localities in glaucophane schist terranes, was synthesized at water pressures of 20–25 kb and temperatures of 550–600 °C under the of the Ni/NiO buffer. The X-ray powder diagram, lattice constants and infrared spectrum of the synthetic phase are closely similar to those of the natural mineral. A solid solution series extends from this ferri-deerite end member to some 20 mole % of a hypothetical alumino-deerite, Fe ₁₂ ²⁺ Al ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀. The upper temperature breakdown of ferri-deerite to the assemblage ferrosilite +magnetite+quartz+water occurs at about 490 °C at 15 kb, and 610 °C at 25 kb fluid pressure for the of the Ni/NiO buffer. Extrapolation of these data to lower water pressures indicates that deerite can be a stable mineral only in very low-temperature, high-pressure environments.     

Fe2⇄Mg2 and TiAl2⇄MgSi2 exchange reactions between clinopyroxenes and silicate melts

The interdependence of the Fe(Mg)_–1 (e.g., FeO-MgO in silicate melt; CaFeSi₂O₆-CaMgSi₂O₆ in pyroxene) and TiAl₂(MgSi₂)_–1 exchange reactions between silicate melts and coexisting Ca-pyroxene has been examined. High-calcium clinopyroxenes were grown in 1 atmosphere melting and crystallization experiments on rock powders spanning the composition range tholeiite to melilitite (1,0922+Mg²⁺ exchange and suggest that at given values of extent of Fe(Mg)_–1 substitution is strongly coupled with the TiAl₂(MgSi₂)_–1 substitution in pyroxenes near the five-component space CaMg(Si₂O₆-CaFe(Si)₂O₆-CaTi(Al)₂O₆-CaFe(Al,Si)₂O₆-CaAl(Al,Si)₂O₆. The inferred stabilization of Ti in iron-rich relative to magnesium pyroxene is consistent with the operation of Fe²⁺Ti⁴⁺ intervalence charge transfer interactions (e.g., Rossman 1980) and observations on zoning in natural titanaugites (e.g., Tracy and Robinson 1977). Although the rims of some pyroxenes grown in some melting experiments exhibit prominent zoning in TiAl₂(MgSi₂)_–1, the average values of inferred from the compositions of these pyroxenes, together with those of the relatively homogeneous pyroxenes produced in crystallization experiments, exhibit a 11 correlation with values of derived from the solution model of Ghiorso et al. (1983) with a standard error of 750 calories. The Ti contents of Ca-rich pyroxenes crystallizing from a wide range of natural silicate liquids can therefore be predicted.     

Synthetic dumortierite: its PTX-dependent compositional variations in the system Al2O3-B2O3-SiO2-H2O

Dumortierite, generally simplified as Al₇BSi₃O₁₈, was synthesized in the pure system Al₂O₃–B₂O₃–SiO₂–H₂O (ABSH) using gels with variable Al/Si ratios mixed with H₃BO₃ and H₂O in known proportions as starting materials. Synthesis conditions ranged from 3 to 5 and 15 to 20 kbar fluid pressure at 650° to 880°C. On the basis of analyses, synthetic dumortierite shows relatively narrow homogeneity ranges with regard to Al/Si which, however, vary as a function of pressure: at low pressures (3–5 kbar) Al/Si is 2.77–2.94 versus 2.33–2.55 at high pressures (15–20 kbar). Outside of these homogeneity limits, dumortierite was found to coexist with quartz or corundum, depending on the starting composition. Whereas synthetic dumortierite invaribly contains 1.0 boron atom per formula unit (p.f.u.) based on 18 oxygens, the water contents vary drastically as a function of pressure and temperature (1.32–2.30 wt.% H₂O or 0.85–1.47 H p.f.u.). H₂O is an essential component in dumortierite. Structural formulae based on complete chemical analyses of the dumortierites synthesized reveal that there is invariably an Si-deficiency against the ideal number of 3.0 p.f.u. In the calculation procedure used here, this deficiency is balanced by assuming tetrahedral Al. The remaining Al, taken to occupy the octahedral sites, is always below the ideal number of 7.0 p.f.u. Charge-balancing the structure with the hydrogen found analytically leads to two different mechanisms of H incorporation: (1) 3H⁺ + octahedral vacancy for Al^[6]; (2) H⁺ + tetrahedral Al for Si^[4]. Dumortierite synthesized at high fluid pressure contains little Al^[4] and, thus, little H⁺ of type 2; its hydrogen is predominantly present as type 1. Conversely, dumortierite formed at low fluid pressures is high in Al^[4] and hydrogen type 2. The amounts of hydrogen type 1 in low-pressure dumortierites decrease with rising temperatures of synthesis. Typical structural formulae are: (Al_6.670.33)[Al_0.49Si_2.51–O_13.53(OH)_1.47](BO₃) for a low-pressure product, and (Al_6.680.32)[Al_0.09Si_2.91O_13.94(OH)_1.06](BO₃) for a high-pressure product. Independently of the synthesis conditions, dumortierite was found always to be orthorhombic, with b₀/a₀ deviating slightly, but significantly from the valid for hexagonal lattice geometry. As a function of increasing Al/Si in the synthetic crystals, their a₀, c₀, and V₀ rise, whereas b₀ decreases. Thus b₀/a₀ decreases most sensitively with rising Al/Si and also with growing Al^[4]. More experimentation is required before the compositional variations of dumortierite found here can be applied successfully to geothermobarometry of natural rocks.     

Spinel-pyroxene-garnet relationships and their dependence on Cr/Al ratio

The partitioning of Cr and Al between coexisting spinel and clinopyroxene and the dependence of spinel-cpxgarnet equilibria on Cr/Al ratio have been investigated by a combination of phase equilibrium experiments, high temperature solution calorimetry and thermodynamic calculations.The exchange equilibrium: has a measured enthalpy change for pure phases of –2,100±500 cal at 970 K and 1 atm. Experimental reversals of Cr-Al partitioning between the spinel and clinopyroxene phases yield the following partitioning relationship: where X _i ^j refers to atomic fraction of i in the octahedral sites of phase j. The compositional dependence of partitioning implies that Al-Cr mixing in spinel is nonideal with, on the symmetrical model, a W _Cr-Al ^Sp of 2,700±500 cal/gm. atom. In contrast, aluminum-chromium mixing in clinopyroxene is close to ideal.The measured stability field of knorringite (Mg₃Cr₂Si₂O₁₂) and mixing properties of garnet have been used in conjunction with our experimental data to calculate the influence of Cr/Al ratio on the important reaction: orthopyroxene+clinopyroxene+spinel=olivine+garnetThe stability field of spinel lherzolite increases by about 2.8 Kb for every increase of 0.1 in Cr/(Cr+Al) ratio up to Cr/(Cr+Al) of 0.7. The calculated stabilization is in very good agreement with the experimental results of O'Neill (1981). The partitioning relationships are such that, at the low ratios of Cr/Al (0.07) of primitive lherzolite, clinopyroxene buffers spinel composition and sharpens the spinelgarnet reaction interval from 10 Kb (little or no clinopyroxene) down to about 2 Kb in pyroxene-rich pyrolite.     

Thorium sorption in the marine environment: Equilibrium partitioning at the hematite/water interface,sorption/desorption kinetics and particle tracing

Thorium(IV) sorption onto hematite (-Fe₂O₃) was examined as a function of pH and ionic strength. Sorption behaved Langmuirian over an eleven order of magnitude range in adsorption densities, : 10^–12 to 10^–1 moles Th sorbed per mole hematite sites, indicating that the overall free energy of Th adsorption is independent of adsorption density. Modeling of Th sorption was conducted with the Triple Layer Model of Davis and Leckie; reactions considered included solution-phase hydroxy and carbonato complexes of thorium, and carbonate/hematite surface complexes. The entire Th sorption isotherm can be modeled with a single surface complex formation reaction

Synthesis and characterization of Mn-bearing ilvaite CaFe 2−x 2+ MnxFe3+ [Si2O7/O/(OH)]

Summary Synthesis of Mn-bearing ilvaites, CaFe _2–x ²⁺ Mn_xFe³⁺ [Si₂O₇/O/(OH)], with 0 x 0.19, have been performed under hydrothermal conditions at 2 and 3 kbars, T = 300 -400°C and at oxygen fugacities defined by the Fe₂O₃/Fe₃O₄ - and the Ni/NiO -buffer. As shown by X-ray diffraction, the substitution of Fe²⁺ by Mn²⁺ decreases the monoclinic angle and causes a phase transition from monoclinic to orthorhombic at x = 0.19. The Fe-distribution has been determined by Mössbauer spectroscopy.

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Synthese und Charakterisierung von Mn-haltigem Ilvait CaFe _2–x ²⁺ Mn_xFe³⁺ [Si₂O₇/O/(OH)]

Zusammenfassung Mn-haltiger Ilvait CaFe _2–x ²⁺ Mn_x Fe³⁺ [Si₂O₇/O/(OH)] wurde unter hydrothermalen Bedingungen bei Drucken von 2 und 3 kbar, Temperaturen zwischen 300 und 400°C und bei Sauerstoff Fugazitäten, die durch Festkörperpuffer (Fe₂O₃/Fe₃O₄ und Ni/NiO) kontrolliert wurden, hergestellt. Röntgenbeugungsuntersuchungen zeigen, daß mit steigendem Mn-Einbau der monokline Winkel kleiner wird, und daß bei x = 0.19 ein Phasenübergang von der monoklinen zur orthorhombischen Struktur erfolgt. Die Fe-Verteilung wurde mit Mössbauer-Spektroskopie bestimmt.

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Schorlomite: a discussion of the crystal chemistry, formula, and inter-species boundaries

Examination of schorlomite from ijolite at Magnet Cove (USA) and silicocarbonatite at Afrikanda (Russia), using electron-microprobe and hydrogen analyses, X-ray diffraction and Mössbauer spectroscopy, shows the complexity of substitution mechanisms operating in Ti-rich garnets. These substitutions involve incorporation of Na in the eightfold-coordinated X site, Fe²⁺ and Mg in the octahedrally coordinated Y site, and Fe³⁺, Al and Fe²⁺ in the tetrahedrally coordinated Z site. Substitutions Ti⁴⁺Fe³⁺Fe³⁺_–1Si_–1 and Ti⁴⁺Al³⁺Fe³⁺_–1Si_–1 are of major significance to the crystal chemistry of schorlomite, whereas Fe²⁺ enters the Z site in relatively minor quantities (<3% Fe). There is no evidence (either structural or indirect, such as discrepancies between the measured and calculated Fe²⁺ contents) for the presence of ^[6]Ti³⁺ or ^[4]Ti⁴⁺ in schorlomite. The simplified general formula of schorlomite can be written as Ca₃Ti⁴⁺₂[Si_3-x(Fe³⁺,Al,Fe²⁺)_xO₁₂], keeping in mind that the notion of end-member composition is inapplicable to this mineral. In the published analyses of schorlomite with low to moderate Zr contents, x ranges from 0.6 to 1.0, i.e. Ti⁴⁺ in the Y site is <2 and accompanied by appreciable amounts of lower-charged cations (in particular, Fe³⁺, Fe²⁺ and Mg). For classification purposes, the mole percentage of schorlomite can be determined as the amount of ^[6]Ti⁴⁺, balanced by substitutions in the Z site, relative to the total occupancy in the Y site: (^[6]Ti⁴⁺–^[6]Fe²⁺–^[6]Mg²⁺– ^[8]Na⁺)/2. In addition to the predominant schorlomite component, the crystals examined in this work contain significant (>15 mol.%) proportions of andradite (Ca₃Fe³⁺₂Si₃O₁₂), morimotoite (Ca₃Fe²⁺TiSi₃O₁₂), and Ca₃MgTiSi₃O₁₂. The importance of accurate quantitative determination and assignment of Fe, Ti and other cations to the crystallographic sites for petrogenetic studies is discussed.

The crystal structure of 2O brittle mica: Anandite

Summary Anandite has an approximate formula of Ba(Fe³⁺, Fe²⁺)₃[Si₂(Fe³⁺, Fe²⁺, Si)₂O_10–x(OH)_x] (S, Cl) (OH), withx=0–1, and belongs to the 2 O brittle mica group. It is orthorhombic; space groupPnmn;a=5.468(9) Å,b=9.489(18)Å,c=19.963(11) Å;Z=4.The structure was determined from 3dim. Weissenberg-data, starting with an approximate structure in the pseudo space groupCcmm. Least squares refinement resulted inR=0.061 for 409 photometric intensities, andR=0.131 for all 853 observedhkl-reflexions.The iron of the tetrahedral layer is concentrated in one of the two crystallographically different kinds of tetrahedra. The basal oxygen rings of the tetrahedral layer form approximate hexagons and have not the ditrigonal configuration of the common micas. This peculiarity is considered to be a consequence of the size and charge of the barium ion. The role of OH in the common micas is played partly by S^2– and Cl^– in anandite.

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Die Kristallstruktur des 2 O Sprödglimmers Anandit

Zusammenfassung Anandit hat die ungefähre Formel Ba(Fe³⁺, Fe²⁺)₃[Si₂(Fe³⁺, Fe²⁺, Si)₂O_10–x(OH)_x] (S, Cl) (OH) mitx=0–1 und gehört zur 2O Sprödglimmergruppe. Er ist rhombisch; RaumgruppePnmn; a=5,468(9) Å,b=9,489(18) Å,c=19,963(11) Å;Z=4.Die Struktur wurde aus Weissenberg-Daten bestimmt, wobei mit einer approximativen Struktur in der PseudoraumpruppeCcmm begonnen wurde. Die Verfeinerung nach der Methode der kleinsten Quadrate führte für 409 photometrierte Reflexe aufR=0,061 und für alle 853 beobachtetenhkl-Reflexe aufR=0,131.Der Eisengehalt der Tetraederschicht ist in einer der beiden kristallographisch verschiedenen Tetraederarten konzentriert. Die basalen Sauerstoffringe der Tetraederschicht bilden annäherungsweise Sechsecke und haben nicht die ditrigonale Konfiguration der gewöhnlichen Glimmer. In Anandit spielen S^2– und Cl^– teilweise die Rolle der Hydroxylgruppen in den gewöhnlichen Glimmern.

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Amphibole composition in tonalite as a function of pressure: an experimental calibration of the Al-in-hornblende barometer

The Al-in-hornblende barometer, which correlates Al^tot content of magmatic hornblende linearly with crystallization pressure of intrusion (Hammarstrom and Zen 1986), has been calibrated experimentally under water-saturated conditions at pressures of 2.5–13 kbar and temperatures of 700–655°C. Equilibration of the assemblage hornlende-biotite-plagioclase-orthoclasequartz-sphene-Fe-Ti-oxide-melt-vapor from a natural tonalite 15–20° above its wet solidus results in hornblende compositions which can be fit by the equation: P(±0.6 kbar) = –3.01 + 4.76 Al _hbl ^tot r ²=0.99, where Al^tot is the total Al content of hornblende in atoms per formula unit (apfu). Al^tot increase with pressure can be ascribed mainly to a tschermak-exchange ( ) accompanied by minor plagioclase-substitution ( ). This experimental calibration agrees well with empirical field calibrations, wherein pressures are estimated by contact-aureole barometry, confirming that contact-aureole pressures and pressures calculated by the Al-in-hornblende barometer are essentially identical. This calibration is also consistent with the previous experimental calibration by Johnson and Rutherford (1989b) which was accomplished at higher temperatures, stabilizing the required buffer assemblage by use of mixed H₂O-CO₂ fluids. The latter calibration yields higher Al^tot content in hornblendes at corresponding pressures, this can be ascribed to increased edenite-exchange ( ) at elevated temperatures. The comparison of both experimental calibrations shows the important influence of the fluid composition, which affects the solidus temperature, on equilibration of hornblende in the buffering phase assemblage.     

Correlation of irradiation-induced yellow color with the O<Superscript>−</Superscript> hole center in tourmaline

Tourmaline with the general formula XY₃Z₆(BO₃)₃Si₆O₁₈(OH,O)₃(OH,F) and the trigonal space group R3m (C_3v⁵) is known as a gemstone with great variety of colors. Some color centers are related to transition metal ions, and others to electron or hole traps. In this paper we report on a combined study using electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and the optical detection of EPR (ODEPR) on a yellow color center produced by -irradiation in colorless Li-bearing elbaite tourmaline from Brazil. The color center is an O^– hole trap center, which is stabilized within the plane spanned by three Y sites, and is located in the structural channels formed by Si₆O₁₈. We suggest that two of the Y sites are substituted by ²⁷Al and the other by ^6,7Li. During the irradiation process atomic hydrogen H⁰ is also produced, which shows the same thermal stability as the hole center (250 °C). Therefore, we assign H⁰ to be the local charge compensator for the hole trap. From the ODEPR measurements we conclude that the yellow color is caused by the O^– hole center. The large negative isotropic Al superhyperfine interaction of the O^– hole trap center is consistent with a calculation of the transferred hyperfine interactions by exchange polarization supporting the proposed defect model of an O^– at the O₁ sites, whereby the O^– is relaxed into the plane formed by three Y ions.     

A thermodynamic model of Fe–Cr spinels

A new thermodynamic model for multi-component spinel solid solutions has been developed which takes into account thermodynamic consequences of cation mixing in spinel sublattices. It has been applied to the evaluation of thermodynamic functions of cation mixing and thermodynamic properties of Fe₃O₄–FeCr₂O₄ spinels using intracrystalline cation distribution in magnetite, lattice parameters and activity-composition relations of magnetite–chromite solid solutions. According to the model, cation distribution in binary spinels, (Fe_1-x²⁺ Fe_x³⁺)[Fe_x²⁺Fe_2-2y-x³⁺Cr_2y]O₄, and their thermodynamic properties depend strongly on Fe²⁺–Cr³⁺ cation mixing. Mixing of Fe²⁺–Fe³⁺ and Fe³⁺–Cr³⁺ can be accepted as ideal. If Fe²⁺, Fe³⁺ and Cr are denoted as 1, 3 and 4 respectively, the equation of cation distribution is –RT ln(x²/((1–x)(2–2y–x)))= G₁₃^* + (1–2x)W₁₃+y(W₁₄–W₁₃–W₃₄) where G₁₃^* is the difference between the Gibbs energy of inverse and normal magnetite, W_ij is a Margules parameter of cation mixing and G₁₃^*, J/mol =–23,000+13.4 T, W₁₄=36 kJ/mol, W₁₃=W₃₄=0. The positive nonconfigurational Gibbs energy of mixing is the main reason for changing activity–composition relations with temperature. According to the model, the solvus in Fe₃O₄–FeCr₂O₄ spinel has a critical temperature close to 500°C, which is consistent with mineralogical data.     

The stability and phase relations of iron chlorite below 8.5 kb P_{{\text{H}}_{\text{2}} {\text{O}}}

Iron chlorites with compositions intermediate between the two end-members daphnite (Fe₅Al₂Si₃O₁₀(OH)₈) and pseudothuringite (Fe₄Al₄Si₂O₁₀(OH)₈) were synthesized from mixtures of reagent chemicals. The polymorph with a 7 Å basal spacing initially crystallized from these mixtures at 300 °C and 2 kb after two weeks. Conversion to a 14 Å chlorite required a further 6 weeks at 550 °C. Shorter conversion times were required at higher water pressures. The products contained up to 20% impurities.The maximum equilibrium decomposition temperature for iron chlorite, approximately 550 °C at 2kb, is at an between assemblages (1) and (2) listed below. Synthetic iron chlorite will break down by various reactions with variable P, T, and fugacity of oxygen. For the composition FeAlSi = 523, the sequence of high temperature breakdown products with increasing traversing the magnetite field for P _total = =2kb is: (1) corierite+ fayalite+hercynite; (2) cordierite+fay alite+magnetite; (3) cordierite+magnetite+quartz; (4) magnetite+mullite+quartz. Almandine should replace cordierite in assemblages (1) and (2) but it did not nucleate. The significance of the relationship between iron cordierite and almandine in this system is discussed.At water pressures from 4 to 8.5 kb and at the nickel-bunsite buffer, iron chlorite+quartz break down to iron gedrite+magnetite with temperature 550 to 640 °C along the curve. At temperatures 50 °C greater and along a parallel curve, almandine replaces iron gedrite. For on this buffer curve, almandine is unstable below approximately 4 kb for temperatures to approximately 750 °C.     

Die Kristallstruktur des Ferrinatrits,Na3Fe[SO4]3 · 3H2O

Zusammenfassung Die Kristallstruktur des Ferrinatrits, Na₃Fe[SO₄]₃·3H₂O, Raumgruppe ,a _o=15,560 Å,c _o=8,666 Å,Z=6, wurde mittels der mit einem Zweikreis-Diffrak tometer gemessenen Röntgen-Intensitäten bestimmt und für 1591 symmetrieunabhängigeF _obs aufR=0,047 verfeinert. In Ferrinatrit sind FeO₆-Oktaeder und Sulfattetraeder über gemeinsame Ecken zu Ketten verknüpft. Diese Ketten verlaufen parallelz und sind untereinander über Natriumionen und Wassermoleküle verbunden. Die Mittelwerte der wichtigsten Bindun gslängen betrgen: Fe–O=1,997 Å, S–O=1,474 Å, Na–(4×O+2×Ow)=2,49 Å.

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The crystal structure of ferrinatrite, Na₃Fe[SO₄]₃ · 3H₂O

Summary The crystal structure of ferrinatrite, Na₃Fe[SO₄]₃·3H₂O, space group ,a ₀=15.560 Å,c ₀=8.666 Å,Z=6, was determined from X-ray intensities measured on a 2-circle diffractometer and was refined using 1591 independentF _obs toR=0.047. FeO₆ Octahedra and sulfate tetrahedra share common corners to from infinite chains which run parallel toz and are linked by sodium ions and water molecules. Important average bond lengths are: Fe–O=1.997 Å, S–O=1.474Å, Na-(4×0+2×Ow)=2.49 Å.

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Mit 2 Abbildungen

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Herrn Prof. DDr.H. Wieseneder zum 70. Geburtstag gewidmet.     

The crystal structure of a triclinic roscherite

Summary The crystallography of roscherite is more complicated than previously thought. Single crystal X-ray work on material from Foote Mine (California) gave triclinic symmetry. The unit cell corresponding to the one adopted for monoclinic roscherite hasa=15.921,b=11.965,c=6.741 Å, =91°04, =94°21, =89°59 1/2, space group . The least-squares refinement of the structure using 2380 non zero reflections with anisotropic temperature factors resulted in a conventional reliability factorR=0.060.The X-ray study indicates the formula while that proposed for monoclinic roscherite is The atomic arrangements of both varieties of roscherite are very similar. The lowering of symmetry is caused by the segregation of the trivalent cations into only half of the sites of a monoclinic point position. Crystallochemical considerations suggest that the symmetry of roscherite does not depend on the kind of trivalent cations occupying the 6-coordinated position, but rather by the ratio between trivalent and divalent metal ions.

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Die Kristallstruktur eines triklinen Roscherites

Zusammenfassung Die Kristallographie des Roscherites ist komplizierter als man bisher annahm. Einkristall-Röntgenuntersuchungen an Material von Foote Mine (Kalifornien) ergaben trikline Symmetrie. Die Elementarzelle, welche der für monoklinen Roscherit angenommenen entspricht, hata=15,921,b=11,965,c=6,741 Å, =91°04, =94°21, =89°59 1/2, Raumgruppe . Die Verfeinerung der Struktur mit der Methode der kleinsten Quadrate ergab unter Verwendung anisotroper Temperaturfaktoren für 2380 beobachtete Reflexe einen konventionellen ZuverlässigkeitsindexR=0,060.Die Röntgenuntersuchung weist auf die Formel , während für monoklinen Roscherit vorgeschlagen wurde. Die Atomanordnungen beider Abarten des Roscherites sind sehr ähnlich. die Symmetrieerniedrigung wird dadurch hervorgerufen, daß die dreiwertigen Kationen nur die Hälfte der Positionen einer monoklinen Punktlage besetzen. Kristallchemische Überlegungen weisen darauf hin, daß die Symmetrie nicht von der Art der dreiwertigen Kationen, welche eine 6-koordinierte Punktlage besetzen, abhängt, sondern vielmehr von dem Mengenverhältnis zwischen 3-wertigen und 2-wertigen Metallionen.

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Systematic study of liquidas phase relations in olivine melilitite +H2O +CO2 at high pressures and petrogenesis of an olivine melilitite magma

Near-liquidus phase relationships of a spinel lherzolite-bearing olivine melilitite from Tasmania were investigated over a P, T range with varying , , and . At 30 kb under MH-buffered conditions, systematic changes of liquidus phases occur with increasing ( = CO₂/CO₂ +H₂O+olivine melilitite). Olivine is the liquidus phase in the presence of H₂O alone and is joined by clinopyroxene at low . Increasing eliminates olivine and clinopyroxene becomes the only liquidus phase. Further addition of CO₂ brings garnet+orthopyroxene onto the liquidus together with clinopyroxene, which disappears with even higher CO₂. The same systematic changes appear to hold at higher and lower pressures also, only that the phase boundaries are shifted to different . The field with olivine- +clinopyroxene becomes stable to higher with lower pressure and approaches most closely the field with garnet+orthopyroxene+clinopyroxene at about 27 kb, 1160 °C, 0.08 and 0.2 (i.e., 6–7% CO₂+ 7–8% H₂O). Olivine does not coexist with garnet+orthopyroxene+clinopyroxene under these MH-buffered conditions. Lower oxygen fugacities do not increase the stability of olivine to higher and do not change the phase relationships and liquidus temperatures drastically. Thus, it is inferred that olivine melilitite 2927 originates as a 5% melt (inferred from K_{2 O} and P₂O₅ content) from a pyrolite source at about 27kb, 1160 dg with about 6–7% CO₂ and 7–8% H₂O dissolved in the melt. The highly undersaturated character of the melt and the inability to find olivine together with garnet and orthopyroxene on the liquidus (in spite of the close approach of the respective liquidus fields) can be explained by reaction relationships of olivine and clinopyroxene with orthopyroxene, garnet and melt in the presence of CO₂.     

The pleochroism of a gem-quality enstatite in the region of the OH stretching frequency,with a stereochemical interpretation

Summary The pleochroic behaviour of a gem-quality enstatite from Tanzania was investigated in the region =2500 to 4000 cm^–1. Two sharp absorption bands at =3410 cm^–1 and =3510 cm^–1 are interpreted to be caused by OH stretching vibrations. As their absorption coefficients are considerably larger parallel to [001] (=direction of the silicate chains) than perpendicular to this direction, the OH dipoles have to be oriented approximately parallel to [001]. On this basis, a stereochemical interpretation of the incorporation of the OH groups into the structure is given.

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Der Pleochroismus eines Enstatits von Edelsteinqualität im Gebiet der OH-Streckfrequenz und seine kristallchemische Interpretation

Zusammenfassung Das pleochroitische Verhalten eines Enstatits von Edelsteinqualität aus Tansania wurde im Bereich =2500 bis 4000 cm^–1 untersucht. Von zwei scharfen Banden bei =3410 cm^–1 und 3510 cm^–1 wird angenommen, daß sie durch OH-Streckschwingungen herrühren. Da ihre Absorptionskoeffizienten parallel zu [001] (=Richtung der Silikatketten) beträchtlich größer sind als senkrecht dazu, müssen die OH-Dipole ungefähr parallel zu [001] liegen. Auf dieser Basis wird der Einbau der OH-Gruppen in die Struktur diskutiert.

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With 3 Figures     

Machatschkiit,ein neues Arsenatmineral aus der Grube Anton im Heubachtal bei Schiltach (Schwarzwald,Bundesrepublik Deutschland)

Zusammenfassung Machatschkiit ist ein neues wasserhaltiges Calciumarsenat, das in der Grube Anton bei Schiltach im mittleren Schwarzwald (BRD) 1960 gefunden wurde. Es kommt zusammen mit Gips, Pharmakolith, Pikropharmakolith und Sainfeldit als Sekundärbildung krustenförmig auf Granit vor.Als charakteristische Form tritt das Rhomboeder auf. Keine Spaltbarkeit, Bruch muschelig, Härte 2–3,G=2,5 bis 2,6 g·cm^–3,D _x =2,50 g·cm^–3, farblos, durchsichtig bis durchscheinend. Optische Daten:n =1,585±0,002,n =1,593±0,002, einachsig oder schwach zweiachsig, negativ.Gitterkonstanten:a ₀=15,10,c ₀=22,59 Å,a ₀c ₀=11,4960,Z=12;a _rh =11,52 Å, =81°52,Z=4. Mögliche Raumgruppen:R32,R3m, . Stärkste Linien des Pulverdiagramms: 8,59 (10) (110), 5,34 (8) (210), 3,59 (8) . Eine chemische Analyse ergab nach Umrechnung folgende Zusammensetzung: CaO 29,5%, As₂O₅ 40,8%, SO₃ 0,5%, H₂O 29,2%, Summe 100,0%. Dies kommt der Formel Ca₃(AsO₄)₂ · 9 H₂O sehr nahe. In verdünnter HCl und HNO₃ ist der Machatschkiit leicht löslich.

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Machatschkiite, a new arsenate mineral from the Anton Mine in the Heubach valley near Schiltach (Black Forest, Federal Republic of Germany)

Summary Machatschkiite is a new hydrous calcium arsenate which was found 1960 in the Anton Mine near Schiltach in the central Black Forest. It is a secondary mineral which occurs in crusts on granite in association with gypsum, pharmacolite, picropharmacolite and sainfeldite.The characteristic form is the rhombohedron . No cleavage, fracture conchoidal, hardness 2–3,G=2.5–2.6 g·cm^–3,D _x =2.50 g·cm^–3, colourless, transparent to translucent. Optical data:n =1.585±0.002,n =1.593±0.002, uniaxial or weakly biaxial, negative.Unit-cell dimensions:a ₀=15.10,c ₀=22.59 Å,a ₀c ₀=11.4960,Z=12;a _rh =11.52 Å, =81°52,Z=4. Possible space groups:R32,R3m, . Strongest lines of the powder pattern: 8.59 (10) (110), 5.34 (8) (210), 3.59 (8) . A chemical analysis gave the following composition after recalculation: CaO 29.5%, As₂O₅ 40.8%, SO₃ 0.5%, H₂O 29.2%, total 100.0%. This agrees well with the formula Ca₃(AsO₄)₂ · 9 H₂O. Machatschkiite is easily soluble in diluted HCl and HNO₃.

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Mit 3 Abbildungen     

The restricted stability of osumilite under hydrous conditions in the system K2O-MgO–Al2O3–SiO2–H2O

Osumilite_ss was synthesized as a single phase product in the model system K₂O-MgO-Al₂O₃-SiO₂ at 800° C/ 0.5 Kbar water pressure and at 800° to 840° C/1.0 Kbar total pressure with 0.3 in the gas phase. The experimentally determined solid solubility range of synthetic osumilites can be expressed by the formula KMg₂(Al_3-xMg_x) (Al_2–xSi_10+x)O₃₀ with 0x0.4. A survey of sixteen chemical analyses of natural osumilites from eleven occurrences shows a solid solubility characterized by 0x0.6. Reversed stability experiments for the synthetic osumilite KMg₂(Al_2.75Mg_0.25)(Al_1.75Si_10.25)O₃₀ determined at water pressure equal to total pressure demonstrate its restriction to water pressures below 0.8 Kbar (at 0.5 Kbar, the stability range is between 765° and 800° C). At the lower thermal stability limit osumilite+H₂O vapor break down to cordierite+K feldspar+phlogopite_ss+quartz, at the higher one to cordierite+K feldspar+phlogopite+liquid. Reduction of water fugacity will expand the stability field largely by shifting the lower and higher thermal stability limits to lower and higher temperatures, respectively. The dependence of osumilite stability on water fugacity makes osumilite a sensitive indicator mineral for dry conditions in rocks formed at total pressures higher than about 0.8 Kbar.     

An experimental study of the diffusion of oxygen in quartz and albite using an overgrowth technique

Diffusion rates of¹⁸O tracer in quartz ( c, 1 Kb H₂O) and Amelia albite ( 001, 2 Kb H₂O) have been measured, using Secondary Ion Mass Spectrometry (SIMS). A new technique involving hydrothermal deposition of labelled materials has removed the possibility of pressure solution-reprecipitation processes adversely affecting the experiments. Reported diffusion constants are:-quartz ( c), ,Q=98±7 KJ mol^–1 (600–825° C, 1 Kb); Amelia albite ( 001), ,Q=85±7 KJ mol^–1, (400–600° C, 2 Kb). Measured quartz¹⁸O diffusivities decrease discontinuously at the- transition, reflecting strong structural influences. The reported albite data agree with previously recorded studies, but-quartz data indicate significantly lower activation energies. Possible causes of this discrepancy, and some geological consequences, are noted.