Thermal expansion,heat capacity,and entropy of MgO at mantle pressures

The pressure dependence of the Raman spectrum of forsterite was measured over its entire frequency range to over 200 kbar. The shifts of the Raman modes were used to calculate the pressure dependence of the heat capacity, C _v, and entropy, S, by using statistical thermodynamics of the lattice vibrations. Using the pressure dependence of C _v and other previously measured thermodynamic parameters, the thermal expansion coefficient, , at room temperature was calculated from = K _S (T/P) _S C _V/TVK _T, which yields a constant value of ( ln / ln V)_T= 6.1(5) for forsterite to 10% compression. This value is in agreement with ( ln / ln V)_T for a large variety of materials.At 91 kbar, the compression mechanism of the forsterite lattice abruptly changes causing a strong decrease of the pressure derivative of 6 Raman modes accompanied by large reductions in the intensities of all of the modes. This observation is in agreement with single crystal x-ray diffraction studies to 150 kbar and is interpreted as a second order phase transition.     

Johillerit,Na(Mg,Zn)3 Cu(AsO4)3, ein neues Mineral aus Tsumeb,Namibia

Zusammenfassung Die chemische Analyse des neuen Minerals Johillerit mit der Elektronenmikrosonde ergab: Na₂O 5,4, MgO 18,3, ZnO 5,4, CuO 15,8 und As₂O₅ 55,8, Summe 100.7%. Aus diesem Ergebnis wurde die idealisierte Formel Na(Mg, Zn)₃ Cu(AsO₄)₃ abgeleitet. Johillerit ist monoklin mit der RaumgruppeC2/c. Die Gitterkonstanten sind:a=11,870 (3),b=12,755 (3),c=6,770 (2) , =113,42 (2)°,Z=4. Die stärksten Linien des Pulverdiagramms sind: 4,06 (5) (22 ), 3,50 (4) (310), 3,25 (8) (11 ), 2,75 (10) (330, 240), 2,64 (5) (311, 13 , 40 ), 1,952 (4) (13 , 35 ), 1,682 (4) (20 , 460), 1,660 (5) (40 , 71 , 550, 64 ), 1,522 (4) (442, 153, 13 ). Es bestehen enge strukturelle Beziehungen zwischen Johillerit und O'Danielit, Na(Zn, Mg)₃H₂(AsO₄)₃, sowie einigen synthetischen. Verbindungen.Johillerit ist violett durchscheinend. Die Spaltbarkeit nach {010} ist ausgezeichnet und nach {100} und {001} gut.H (Mohs)3.D=4,15 undD _X =4,21 g·cm^–3. Das Mineral ist optisch zweiachsig positiv, 2V80 (5)°. Die Werte der Lichtbrechung sindn =1,715 (4),n =1,743 (4) undn =1,783 (4). Die Auslöschung istn b und auf (010)n c16°. Johillerit ist stark pleochroitisch mit den AchsenfarbenX=violett-rot,Y = blauviolett undZ = grünblau. Das neue Mineral kommt in radialstrahligen Massen gemeinsam mit kupferhaltigem Adamin und Konichalcit in zersetzem Kupfererz von Tsumeb, Namibia, vor. Die Benennung erfolgte nach Prof. Dr.J.-E. Hiller (1911–1972).

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Johillerite, Na(Mg, Zn) ₃ Cu(AsO ₄ ) ₃ , a new mineral from Tsumeb, Namibia

Summary Electron microprobe analysis of the new mineral johillerite gave Na₂O 5.4, MgO 18.3, ZnO 5.4, CuO 15.8, and As₂O₅ 55.8, total 100.7%. From this result, the ideal formula is given as Na(Mg, Zn)₃ Cu(AsO₄)₃. Johillerite crystallizes monoclinic,C2/c. The unit cell dimensions are:a=11.870(3),b=12.755 (3),c=6.770 (2) , =113.42 (2)°,Z=4. The strongest lines on the X-ray powder diffraction pattern are: 4,06 (5) (22 ), 3,50 (4) (310), 3,25 (8) (11 ), 2,75 (10) (330, 240), 2,64 (5) (311, 13 , 40 ), 1,952 (4) (13 , 35 ), 1,682 (4) (20 , 460), 1,660 (5) (40 , 71 , 550, 64 ), 1,522 (4) (442, 153, 13 ). There is a close relationship between johillerite, o'danielite, Na(Zn, Mg)₃H₂(AsO₄)₃, and some synthetic compounds. Johillerite is violet in colour, transparent. Cleavage is {010} perfect, {100} and {001} good.H (Mohs)3.D=4.15 andD _X =4.21 g·cm^–3. The mineral is optically biaxial positive, 2V80 (5)°. The refractive indices are:n =1.715 (4),n =1.743 (4),n =1.783 (4). The extinction isn b and on (010)n c16°. Strongly pleochroic with axial coloursX=violet-red,Y=bluish violet andZ=greenish blue. The new mineral was found in radiated masses together with cuprian adamite and conichalcite in an oxidized copper ore from Tsumeb, Namibia. It is named in honour of Prof. Dr.J.-E. Hiller (1911–1972).

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Mit 1 Abbildung     

Synthesis and some properties of iron- and vanadium-bearing kyanites, (Al,Fe3+)2SiO5and (Al,V3+)2SiO5

Iron- and vanadium-bearing kyanites have been synthesized at 900 and 1100° C/20 kb in a piston-cylinder apparatus using Mn₂O₃/Mn₃O₄- and MnO/Mn-mixtures, respectively, as oxygen buffers. Solid solubility on the pseudobinary section Al₂SiO₅-Fe₂SiO₅(-V₂SiO₅) of the system Al₂O₃-Fe₂O₃(V₂O₃)-SiO₂ extends up to 6.5 mole% (14mole %) of the theoretical end member FeSiO₅(V₂SiO₅) at 900°C/20 kb. For bulk compositions with higher Fe₂SiO₅ (V₂SiO₅) contents the corundum type phases M₂O₃(M = Fe³⁺, V³⁺) are found to coexist with the Fe³⁺(V³⁺)-saturated kyanite solid solution plus quartz. The extent of solid solubility on the join Al₂SiO₅-Fe₂SiO₅ at 1 100°C was not found to be significantly higher than at 900° C. Microprobe analyses of iron bearing kyanites gave no significant indication of ternary solid solubility in these mixed crystals. Lattice constants a ₀, b ₀, c ₀, and V₀ of the kyanite solid solutions increase with increasing Fe₂SiO₅- and V₂SiO₅-contents proportionally to the ionic radii of Fe³⁺ and V³⁺, respectively, the triclinic angles ,, remain constant. Iron kyanites are light yellowish-green, vanadium kyanites are light green. Iron kyanites, (Al_1.87 Fe _0.13 ³⁺ )SiO₅, were obtained as crystals up to 700 m in length.     

Koritnigit,Zn[H2O|HOAsO3], ein neues Mineral aus Tsumeb,Südwestafrika

Zusammenfassung Das neue Mineral Koritnigit ist ein wasserhaltiges Zinkhydrogenarsenat der Formel Zn[H₂O|HOAsO₃]. Die chemische Analyse (Elektronenmikrosonde und T.G.A.) ergab: As₂O₅ 51,75%, ZnO 35,97% und H₂O 12,3%, Summe 100,0%. Die HOAsO₃-Ionen wurden IR-spektroskopisch nachgewiesen. Koritnigit ist löslich in kalter, verdünnter HCl und HNO₃.Die Gitterkonstanten sind:a ₀=7,948(2),b ₀=15,829(5),c ₀=6,668(2) Å, =90,86(2), =96,56(2), =90,05(2)^o,V=833,2(4)ų,V=8. Die Raumgruppe ist . Die stärksten Linien des Pulverdiagramms sind: 7,90(10) (020,100), 3,83(7) ( ), 3,16(9) ( ) 2,926(4) (150), 2,679(4) ( ), 2,461(6) ( ), 2,186(5) ( ), 1,969(4) (400), 1,649(3) (004).Koritnigit ist wasserklar bis durchscheinend weiß. Idiomorphe Kristalle sind nicht bekannt. Die Spaltbarkeit nach {010} ist ausgezeichnet und auf {010} sind Spaltspuren nach [001] und nach [100] erkennbar. Härte 2.G=3,54 g·cm^–3,D _x =3,56 g·cm^–3. Koritnigit ist optisch zweiachsig positiv, 2V70(5)^o. Die Werte der Lichtbrechung sind:n =1,632(5),n =1,652(3) undn =1,693(3).Koritnigit wurde auf der 31. Sohle der Tsumeb-Mine, Südwestafrika gefunden. Er kommt als Sekundärmineral in Paragenese mit Cu-Adamin, Stranskiit und drei weiteren, vorerst nicht identifizierten mineralen in Zersetzungshohlräumen von Tennantit vor.

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Koritnigite, Zn[H₂O|HOAsO₃], a new mineral from Tsumeb, South West Africa

Summary The new mineral koritnigite is a hydrated zinc hydrogen arsenate with the formula Zn[H₂O|HOAsO₃]. Chemical analysis (electron microprobe and t.g.a.) gave: As₂O₅ 51.75%, ZnO 35.97%, and H₂O 12.3%, total 100.0%. The HOAsO₃ ions were determined by IR spectroscopy. Koritnigite is soluble in cold diluted HCl and HNO₃. The unit cell dimensions are:a ₀=7.948(2),b ₀=15.829(5),c ₀=6.668(2)Å, =90.86(2), =96.56(2), =90.05(2)^o,V=833.2(4) ų,Z=8. The space group is . The strongest lines of the powder pattern are: 7.90(10) (020, 100), 3.83(7) ( ), 3.16(9) ( ), 2.926(4) (150), 2.679(4) ( ), 2.461(6) ( ), 2.186(5) ( ), 1.969(4)(400), 1.649(3) (004).

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Mit 2 Abbildungen

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Herrn Univ. Prof. Dr.H. Meixner zum 70. Geburtstag gewidmet.     

Phase transitions in leucite,KAISi2O6

An order parameter treatment of the phase transitions in leucite, KAlSi₂O₆, at approximately 950 and 920 K: (cubic) I4₁ acd(tetragonal) I4₁ a(tetragonal) is presented in terms of Landau theory and induced representation theory. The Al-Si order with decreasing temperature is taken as the primary order parameter to which other distortions (K⁺ ion displacements, strain components, etc.) couple linearly. The expected Al-Si ordering behavior and the associated K⁺ ion displacements for both transitions are derived and the resulting twin domain orientations are listed. The sequence of phase transitions results from a coupling of ₃ ⁺ and ₄ ⁺ representations. The Landau free energy for the five-dimensional reducible representation has been simplified to two components resulting in a linearquadratic coupling of the components. Possible phase diagrams are derived by free energy minimization. The cubic tetragonal transition is first-order, whereas the tetragonal-tetragonal transition may be second order. A tricritical point exists at which the first-order transition changes to second-order.     

Structural relaxation in silicate melts and non-Newtonian melt rheology in geologic processes

The timescale of structural relaxation in a silicate melt defines the transition from liquid (relaxed) to glassy (unrelaxed) behavior. Structural relaxation in silicate melts can be described by a relaxation time, , consistent with the observation that the timescales of both volume and shear relaxation are of the same order of magnitude. The onset of significantly unrelaxed behavior occurs 2 log₁₀ units of time above . In the case of shear relaxation, the relaxation time can be quantified using the Maxwell relationship for a viscoelastic material; _S = _S/G (where _S is the shear relaxation time, G is the shear modulus at infinite frequency and _S is the zero frequency shear viscosity). The value of G known for SiO₂ and several other silicate glasses. The shear modulus, G , and the bulk modulus, K , are similar in magnitude for every glass, with both moduli being relatively insensitive to changes in temperature and composition. In contrast, the shear viscosity of silicate melts ranges over at least ten orders of magnitude, with composition at fixed temperature, and with temperature at fixed composition. Therefore, relative to _S, G may be considered a constant (independent of composition and temperature) and the value of _S, the relaxation time, may be estimated directly for the large number of silicate melts for which the shear viscosity is known.For silicate melts, the relaxation times calculated from the Maxwell relationship agree well with available data for the onset of the frequency-dependence (dispersion) of acoustic velocities, the onset of non-Newtonian viscosities, the scan-rate dependence of the calorimetric glass transition, with the timescale of an oxygen diffusive jump and with the Si-O bond exchange frequency obtained from ²⁹Si NMR studies.     

Formulation of the thermodynamic functions for mantle minerals: MgO as an example

The formulas for thermodynamic functions for minerals are presented, couched in terms of the important thermodynamic variable K_T= (P/T)_v, where is the volume thermal expansivity and K_T is the isothermal bulk modulus. Presenting the formulas in this way leads to simplification since K_T as a product varies only slightly with volume, and is close to being independent of temperature at high temperature. Using our equations, we present as examples some computed data in the form of graphs on the entropy, internal energy, Helmholtz free energy, and Gibbs free energy in the high temperature regime (up to 2000 K) and for high compression (up to 0.7), for MgO. For entropy, knowledge of the V, T dependence of K_T is sufficient. For enthalpy and internal energy, the equation of state is needed in addition.     

β(Mg0.9, Fe0.1)2SiO4: Single crystal structure,cation distribution,and properties of coordination polyhedra

The synthesis boundaries of the phase transformation; ++ in (Mg_0.9, Fe_0.1)SiO₄, have been clarified at temperatures to 2000° C and pressures up to 20 GPa in order to synthesize single crystals of high quality. A single crystal of (Mg_0.9, Fe_0.1)₂SiO₄ was grown successfully to a size of 500 m. The crystal structure has been refined from single-crystal X-ray intensities. The ferrous ions prefer M1 and M3 sites to over the larger M2 site. The volume change of all the occupied polyhedra does not contribute to the decrease of total volume in the transformation; rather it tends to increase the bulk volume through the expansion of occupied tetrahedra. The volume reduction in the phase transformations is accounted for by unoccupied polyhedra, with the octahedra contributory 60% and the tetrahedra 40% to the V of the transition. The volume change in the transformation is caused also partly by the volume decrease of MO ₆ (25%), partly the unoccupied tetrahedra (45%) and octahedra (30%).     

Al-Si ordering in Sr-feldspar SrAl2Si2O8: IR,TEM and single-crystal XRD evidences

Al-Si ordering in Sr-feldspar has been followed by isothermal annealing, starting from a disordered metastable configuration. Ordering could not be followed by changes in the spontaneous strain as cell parameters did not show significant changes with thermal treatment from 0.016 h to 452 h at T=1350° C, while, on the contrary, significant changes in IR spectra are observed. A single crystal obtained from melt (Q _od 0) has been progressively heated up to 678 h at T=1350° C and the relevant structural refinements enabled to monitor changes in degree of Al-Si order up to Q_od = 0.86. In isothermal treatment for Sr-feldspar it is observed a significantly lower Q _od than in anorthite after the same annealing time. TEM observation has shown in Sr-feldspar, also for shortest annealing, b type reflections, while in anorthite, in the same conditions, e type reflections have been observed (Carpenter 1991a). In the first stages of ordering b APDs sized 100 Å (at T=1350° C, 0.33 h) have been observed in Sr-feldspar; APD coarsening occurs with an activation energy of 120±7 kcal mol^-1, not significantly different from anorthite. The ordering process seems to be a slower process in Sr-feldspar than in anorthite, even though data from longer annealing suggest that the Q _od close to the equilibrium is the same in Sr and Ca-feldspar (Q _od = 0.86 at T=1350° C).     

The crystal structure of trigonite,Pb3Mn(AsO3)2(AsO2OH)

Summary The mineral trigonite crystallizes in the monoclinic space groupPn–C _s ² witha ₀=7.26,b ₀=6.78,c ₀=11.09Å; =91.5°,Z=2. The structure was determined from 1250 X-ray intensities collected on an automatic two circle Weissenberg-type diffractometer. The final residual isR=6.5% using anisotropic temperature factors for Pb, Mn and As, and isotropic temperature factors for O.The structure consists of MnO₆ octahedra, sharing all six oxygens with arsenite groups to form a framework. The Pb atoms are attached to this framework with Pb–O distances2.23Å. One oxygen, bound only to an As atom, is interpreted as the donor for a hydrogen bond of 2.75Å.

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Die Kristallstruktur des Trigonits, Pb₃Mn(AsO₃)₂(AsO₂OH)

Zusammenfassung Das Mineral Trigonit kristallisiert monoklin, RaumgruppePn–C _s ² ,a ₀=7,26,b ₀=6,78,c ₀=11,09Å; =91,5°;Z=2. Die Strukturermittlung erfolgte anhand von 1250 Röntgenintensitäten, die auf einem automatischen Zweikreis-Weissenbergdiffraktometer gesammelt wurden. Mit anisotropen Temperaturfaktoren für Pb, Mn und As sowie isotropen für die O-Atome ergibt sich einR-Wert von 6,5%.Die MnO₆-Oktaeder werden über die sechs Sauerstoffe mit Arsenitgruppen zu einem dreidimensionalen Gerüst verknüpft. Über Pb-O-Abstände2,23 Å sind die Pb-Atome in dieses Gerüst eingebaut. Ein Sauerstoff, nur an ein As-Atom gebunden, wird als Donator einer H-Brücke von 2,75 Å interpretiert.

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With 2 Figures     

Mechanisms of the transformations between the α, β and γ polymorphs of Mg2SiO4 at 15 GPa

Data on the mechanisms of mantle phase transformations have come primarily from studies of analogue systems reacted experimentally at low pressures. In order to study transformation mechanisms in Mg₂SiO₄ at mantle pressures, forsterite () has been reacted in the stability field of -phase, at 15 GPa and temperatures up to 900° C, using a multianvil split-sphere apparatus. Transmission electron microscope studies of samples reacted for times ranging from 0.25–5.0 h show that forsterite transforms to -phase by an incoherent nucleation and growth mechanism involving nucleation on olivine grain boundaries. This mechanism and the resultant microstructures are very similar to those observed at much lower pressures in analogue systems (Mg₂GeO₄ and Ni₂SiO₄) as the result of the olivine to spinel () transformation. Metastable spinel () also forms from Mg₂SiO₄ olivine at 15 GPa, in addition to -phase, by the incoherent nucleation and growth mechanism. With time, the spinel progressively transforms to the stable -phase. After 1 h, spinels exhibit a highly striated microstructure along {110} and electron diffraction patterns show streaking parallel to [110] which indicates a high degree of structural disorder. High resolution imaging shows that the streaking results from thin lamellae of -phase intergrown with the spinel. The two phases have the orientation relationship [001]//[001] and [010]//[110] so that the quasi cubic-close-packed oxygen sublattices are continuous between both phases. These microstructures are similar to those observed in shocked meteorites and show that spinel transforms to -phase by a martensitic (shear) mechanism. There is also evidence that the mechanism changes to one involving diffusion-controlled growth at conditions close to equilibrium.     

The crystal structures of CuSO4 · H2O and CuSeO4 · H2O,and their relationships to kieserite

Summary The crystal structures of hydrothermally grown CuSO₄ · H₂O and CuSeO₄ · H₂O were determined by single crystal X-ray methods [Space group ,a = 5.037 (1), 5.129 (1) Å,b = 5.170(1), 5.527(1)Å,c = 7.578(2), 7.469(2)Å, = 108.62(1), 103.98(1)°, = 108.39(1), 106.52(1)°, = 90.93(1), 97.19(1)°; Z = 2; R_w = 0.026, 0.030 for 2065, 2235 reflections with sin / 0.90 Å^–1]. The Cu atoms are [4 + 2]-coordinated to O atoms. These elongated octahedra are corner connected via the H₂O molecule to form chains. The formal units ¹ [Cu₂O₈(H₂O)2]^12- are interconnected by [XO₄]^2- groups (X=S,Se) and hydrogen bonds (bond lengths 2.72–2.83 Å). The crystal structures show pseudomonoclinic symmetry and are strongly related to the structure type of kieserite.[/p]

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Die Kristallstrukturen von CuSO₄ · H₂O und CuSeO₄ · H₂O und ihre Beziehungen zum Kieserit

Zusammenfassung Die Kristallstrukturen von hydrothermal gezüchtetem CUSO₄ · H₂O und CuSeO₄. H₂O wurden an Einkristallen mittels Röntgenbeugung bestimmt [Raumgruppe ;a = 5.037(1), 5.129(1)Å,b = 5.170(1), 5.527(1)Å,c = 7.578(2), 7.469 (2) Å, = 108.62(1), 103.98(1)°, = 108.39(1), 106.52(1)°, = 90.93(1), 97.19(1)°; Z = 2; R_W = 0.026, 0.030 für 2065, 2235 Reflexe mit sin / 0.90)Å^–1]. Die Cu-Atome werden durch O-Atome [4+2]-koordiniert. Diese gestreckten /lOktaeder sind miteinander über Ecken durch die H₂O-Moleküle zu Ketten verknüpft. Die formalen Einheiten ¹ [CU₂O₈(H₂O)₂]^12– werden durch [XO₄]^2–-Gruppen (X = S, Se) und Wasserstoffbrücken (Bindungslängen 2.72–2.83Å) miteinander verbunden. Die Kristallstrukturen zeigen pseudomonokline Symmetrie und sind sehr nahe mit dem Strukturtyp des Kieserits verwandt.

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With 1 Figure     

1Tc-Strontiohilgardit (Ca,Sr)2[B5O8(OH)2Cl] und seine Stellung in der Hilgarditgruppe X2/II[B5O8(OH)2Cl]

Zusammenfassung 1Tc-Strontiohilgardit (Ca, Sr)₂ [B₅O₈(OH)₂,Cl] mit Ca : Sr etwa 1 : 1 ist ein neues Mineral der Hilgarditgruppe. Fundpunkt: Reyersbausen (9° 59,7 E, 51° 36,6 N), Grube Königshall-Hindenburg, Flöz Staßfurt in sylvinitischer Ausbildung.Konstanten : triklin-pedial,a ₀=6,38 Å,b ₀=6,480 Å,c ₀=6,608 Å, =75,4°,=61,2°, =60,5°; tafelige-gestreckte Links- und Re chtskristalle, farblos, wasserunlöslich, piezoelektrisch. Härte 5–7, Dichte 2,99 g cm^–3;n =1,638,n =1,639,n =1,670; 2V =19°.Neue Daten für die Hilgarditgruppe : 2 M (Cc)-Calciumhilgardit (=Hilgardit) =4 Ca₂[B₅O₃(OH)₂Cl], Raumgruppe Cc.3Tc-Calciumhilgardit (=Parahilgardit) = 3 Ca₂[B₅O₃(OH)₂Cl]; trinklin-pedial, ₀=6,31 Å,b =6,484 Å,c ₀=17,50 Å; =84,0°,=79,6°, =60,9°.Die Polymorphiebeziehungen sind geometrisch deutbar durch eine spezielle Art der Polytropie (Stapelung von Links- und Rechtskristallen im Elementarbereich).     

The elasticity of the upper mantle orthosilicates olivine and garnet to 3 GPa

The elastic moduli of single crystals of pyrope-rich garnet and San Carlos olivine have been measured over a 3 GPa pressure range at room temperature. The combination of improved ultrasonic techniques and this large pressure range provide for more reliable characterization of the pressure dependence of acoustic wave velocities than has previously been possible. First and second pressure derivatives of the velocities have been determined within 1 percent and 10 percent respectively. The Hashin-Shtrikman bounds for the pressure dependences of the bulk and shear moduli of the garnet used in this study are; K = 173.6 GPa, K = 4.93, K = –0.28 GPa^–1, G= 94.9 GPa, G = 1.56, G = –0.08 GPa^–1 and the Hashin-Shtrikman least-upper bounds and greatestlower bounds for the pressure dependences of the bulk and shear moduli of the San Carlos olivine are K=129.8 GPa, K = 4.66, K= –0.15 GPa^–1, G = 77.8 GPa, G = 1.93, G = –0.11 GPa^–1 and K = 129.2 GPa, K = 4.63, K= –0.15 GPa^–1 G = 77.3 GPa, G=1.96, G = –0.11 GPa^–1 respectively. The determination of the room-pressure elastic moduli of this pyrope-almandine garnet removes the previously observed anomaly in the predictions of systematic treatments of variations of the elastic moduli of garnets with composition. The determination of the second pressure derivatives of the moduli of garnet and olivine illustrates the importance of these terms in extrapolations to higher pressures — with K/P for these crystals being reduced by 17 percent and 9 percent respectively over the 3 GPa pressure range.     

Altersbeziehungen zwischen Metamorphosen,mechanischen Deformationen und Intrusionen am Südrand des Rhodope-Massivs (Makedonien,Griechenland)

Zusammenfassung Ausgedehnte Granodiorit- und Granitmagmen intrudierten am Südrand des Rhodope-Massivs (Symvolongebirge und Kavala-Gebiet, Nordgriechenland) syntektonisch in bezug auf eine Formung, die durch überwiegend flach nach NE bis ENE tauchende Faltungs- und Scherungsachsen gekennzeichnet ist (B₂-Tektonik). Die metamorphen Hüllgesteine wurden von der B₂-Tektonik ebenfalls kräftig erfaßt. Ihr älteres Gefüge, das durch mittelsteil nach NNW tauchende B₁-Achsen bestimmt war, kommt daher nur noch reliktisch vor. Der Mineralbestand sowohl der Magmatite als auch ihres metamorphen Rahmens wurde im Zuge der B₂-Tektonik retrograd metamorph umgewandelt.Radiometrische Altersbestimmungen lassen erkennen, daß die magmatischen Gesteine spätestens im Oberkarbon kristallisierten, anschließend jedoch wiederholt aufgewärmt wurden. Das Alter der prämagmatischen Metamorphose der Hüllgesteine und der mit dieser in Zusammenhang stehenden B₁-Tektonik kann demnach nicht jünger als kaledonisch sein.

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Extensive granodioritic and granitic magmas were intruded in the southern margin of the Rhodope-Massif (Symvolon mountains and Kavala region, northern Greece). The intrusions took place syntectonically to a deformation which is characterized by predominantly gently NE to ENE plunging fold- and shear-axes (B₂-folding). The mantling rocks, which have been metamorphosed long before this B₂-folding have an older structure which is characterized by mediumly NNW plunging B₁-axes, visible only in relicts. During the B₂-folding the mineral contents of the igneous rocks and their metamorphic mantling rocks have been metamorphosed retrogressively.Radiometric dating indicates that the crystallization of the magmatic rocks have a minimum age of Upper-Carboniferous, but subsequently these rocks were reheated repeatedly. The age of the premagmatic metamorphism of the mantling rocks and that of the related B₁-foldnig, therefore, cannot be younger than Caledonic.

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Résumé Dans la partie sud du massif du Rhodope (montagnes du Symvolon et région de Kavala, Grèce du Nord) existent de grandes intrusions de magmas granodioritiques et granitiques. Les intrusions eurent lieu syntectoniquement au cours d'une phase de déformation caractérisée par des axes de plis et de cisaillement, généralement à plongement faible vers le NE à ENE (tectonique B₂). Les roches encaissantes, qui furent métamorphisées longtemps avant cette phase de tectonique B₂, ont une structure plus ancienne, caractérisée par des axes B₁ plongeant moyennement vers le NNW. Cette structure est reconnaissable seulement dans des parties réiduelles. Durant la tectonique B₂ les roches éruptives et les roches encaissantes métamorphisées subirent un métamorphisme rétrograde.Des datations radiométriques indiquent, pour la cristallisation des roches magmatiques, au minimum un âge Carbonifère supérieur. Dans la suite ces roches furent réchauffées â plusieures reprises. Le métamorphisme plus ancien des roches encaissantes et la tectonique B₁ associée à ce métamorphisme ne peuvent donc pas Être plus récents que l'époque calédonienne.

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Rhodope ( Symrolon Kavala, ) - . , , , , NE ENE (B₂- ). ₂. , B₁ NNW, . , , . , , , , . , - B₁ .

     

Vinciennite and Cu-excess tennantite from the Layo (Cu,Sn, As,Au) epithermal deposit (Southern Peru)

Summary The Layo epithermal deposit, cutting Miocene-Pliocene calc-alkaline volcanites of the Tacaza group, includes a well-developed eastern zone (Vetas 7 and 8) in which brecciated and banded textures are associated with a large, intensely argillized zone containing diaspore and alunite. The vetas contain a typical Cu-As mineralogy of the acid-sulfate type (pyrite, enargite, Cu-excess tennantite, chalcopyrite, covellite) with an associated original stanniferous paragenesis including vinciennite and mawsonite. The vinciennite is close to the ideal end-member (Cu₁₀Fe₄SnAsS₁₆) and the Cu-excess tennantite (Cu₁₁FeAs₄S₁₃) shows a total absence of Zn and Ag; its very specific chemical composition suggests that all the iron is Fe³⁺, equilibrated by Cu⁺ and probably minor Cu²⁺.This particular mineralogical association implies deposition at relatively low temperature (300°C) and high aS₂ (10^–6.5 decreasing to 10^–8.5), from a Cu-S-rich and Fe-Zn-poor fluid. The acid-sulfate epithermal mineralization of the eastern vetas of Layo appears to have preceded an adularia-sericite epithermal mineralization expressed in the western vetas of Layo and also in the nearby large epithermal veins at Orcopampa and Shila. It also supports the genetic relationship that is commonly evoked between porphyry copper and epithermal deposits.

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Le minéralogie originale à vinciente et tennantite riche du gisement épithermal (Cu, Sn, As, Au) de Layo (Sud Péru)

Résumé Le gîte épithermal de Layo est encaissé dans les volcanites calco-alcalines Miocène-Pliocène du groupe de Tacaza. Sa zone orientale renferme des corps minéralisés (Vetas 7 et 8) bien développés, à textures bréchiques et rubanées associées à une large zone intensément argilisée contenant diaspore et alunite.Les vetas présentent une association minéralogique à As-Cu typique des gisements acide-sulfate (pyrite, énargite, tennantite riche en cuivre, chalcopyrite, covellite) et une paragenèse stannifère originale renfermant vinciennite et mawsonite. La vinciennite est proche du pôle théorique (Cu₁₀Fe₄SnAsS₁₆) et la tennantite riche en Cu (Cu₁₁FeAs₄S₁₃) est dépourvue de Zn et de Ag; sa composition chimique suggère que tout le fer se présente sous la forme Fe³⁺, en équilibre avec Cu⁺, avec probablement une participation mineure de Cu²⁺.Cette association minéralogique particulière implique une mise en place sous forte fugacité en soufre (aS₂ = 10^–6.5 décroissant jusqu'à 10^–8.5) à une température relativement basse de l'ordre de 300°C à partir d'un fluide riche en Cu et S et pauvre en Fe et Zn. La minéralisation de type acide-sulfate des vetas orientales de Layo précéderait celles de type adulaire-sericite des vetas occidentales de Layo et des gisements voisins de Orcopampa et Shila. Elle contribue à renforcer le lien fréquemment évoqué entre les porphyres cuprifères et les gisements épithermaux.

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With 10 Figures     

Lower Triassic alkaline granites of Central Chile (30‡S) in the high-Andean Cordillera

The Na₂O + K₂O/Al₂O₃ molar ratio (agpaitic index) of Lower Triassic leucogranites samples from the Rios Elqui-Lamarí batholith is close to one which is typical of alkaline granites. Loss of alkalis due to groundwater interaction should have occur causing a depletion of the original peralkalinity.It is assumed that this alkaline magmatism has been generated, during crustal extension period, by partial melting of water undersaturated deep crustal rocks.

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Zusammenfassung Das Mol-VerhÄltnis von Na₂O + K₂/Al₂O₃ (agpaitischer Index) der untertriassischen Leukogranit-Proben des Batholithen vom Rios Elqui-Limari liegt in der NÄhe von 1. Dieses ist typisch für Alkaligranite. Der Verlust von Alkali könnte durch Grundwassereinwirkung zustandegekommen sein, was eine Verringerung der ursprünglichen HyperalkalinitÄt verursacht hat.Es wird angenommen, da\ dieser alkalische Magmatismus in einer Phase der Krustenausdehnung entstanden ist durch partielles Aufschmelzen von wasseruntersÄttigten Gesteinen der Tiefenkruste.

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Resumen Leucogranitos de edad triásica inferior pernecientes al batolito compuesto Ríos Elqui-Limarí están caracterizados por presentar una razón molecular Na₂O + K₂O/Al₂O₃ (índice agpaítico) cercano a uno, propio de los granitos alcalinos. Una probable pérdida de álcalis de estos granitos, provocada por el agua infiltrada, sería causante de una disminución de la peralcalinidad original.Se infiere un mecanismo de fusión parcial de rocas corticales profundas subsaturadas en agua, para la génesis de este magmatismo alcalino en un ambiente tectónico de extensión cortical.

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Na₂O + K₂/l₂₃ - - -- 1. . , . , .

     

A materials failure relation of accelerating creep as empirical description of damage accumulation

A general materials failure relation, , describes accelerating creep of materials with rate coefficients andA, by relating rates of deformation, , to changes in deformation rate, (Voight, 1988). Time of failure can be extrapolated from inverse rate versus time data, and andA may be derived to permit one to calculate the failure time. The method is of value for quantitative hazard assessments.Mechanisms leading to damage accumulation during accelerating creep include creep fracture by stress corrosion and power law lattice deformation. These mechanisms are examined here as phenomenologically related to the materials failure relation. Apparently, both mechanisms favour , where is the parameter of the materials failure relation controlling the sensitivity to accelerating activity. For pure shear governed by power law creep of powerp, under constant load, =2.0 andA=p. Stress corrosion is widely described by Charles' equation, relating crack velocity to stress intensity during subcritical crack growth by the stress corrosion indexn. The relationship betweenn and is given by =(2n–2)/n.     

Heterogeneous deformation resulting from stress gradients in calcite single crystals

The stress gradient calculated from an isotropic elastic approximation does not directly reflect the distribution of permanent deformation in a crystal of the same shape under the same conditions. However, with additional crystallographic constraints, it serves to predict locations where twinning and slip are first activated in a stressed crystal. In this study, thick-walled hollow cylinders were cored from single calcite crystals parallel to 0001 and . One cylinder of each orientation was loaded at room temperature under one of two conditions: internal pressure (P _p )=60 MPa, external pressure (P _c )=100 MPa, or P _p = 20 MPa, P _c = 50 MPa. These conditions would produce a radial stress gradient in an isotropic elastic cylinder. Mechanical twins in the deformed calcite samples had a hexagonal distribution in the 0001 oriented cylinder and an orthorhombic distribution in the oriented cylinder.Zones of dense r-slip dislocations were observed in the cylinder. Calculated resolved shear stresses for r-slip in either cylinder remained far below the published critical resolved shear stress (c.r.s.s.) value. Calculated contributions from twinning back stress and anisotropy do not account for the difference between the resolved shear stress and the c.r.s.s. These results underscore the necessity of considering dislocation activiation stresses rather than c.r.s.s. in quantitative analyses of heterogeneous of deformation in single crystals.