Basal slip and texture development in calcite: new results from torsion experiments

The deformation behavior of calcite has been of longstanding interest. Through experiments on single crystals, deformation mechanisms were established such as mechanical twinning on in the positive sense and slip on and both in the negative sense. More recently it was observed that at higher temperatures slip in both senses becomes active and, based on slip line analysis, it was suggested that slip may occur. So far there had been no direct evidence for basal slip, which is the dominant system in dolomite. With new torsion experiments on calcite single crystals at 900 K and transmission electron microscopy, this study identifies slip unambiguously by direct imaging of dislocations and diffraction contrast analysis. Including this slip system in polycrystal plasticity simulations, enigmatic texture patterns observed in compression and torsion of calcite rocks at high temperature can now be explained, resolving a long-standing puzzle.     

A critical look at representations of urban areas in global maps

According to the UN, the number of urban dwellers is expected to increase from roughly 3.2 billion today to more than 4.9 billion by 2030. An accurate and regularly updated estimate of the extent and spatial distribution of urban land is an important first step in our search for realistic responses to the ecological and social consequences of what promises to be the most rapid urbanization in world history. By employing circa-2000 satellite remote sensing imagery, geographic information systems, and census data, six groups from government and academia in both the EU and the US have created global maps that can be used to describe urban land. We compare these maps from global to sub-national scales, for the first time applying Discrete Global Grids to the problem of global-scale map comparison. Although most of these maps share common data inputs, they differ by as much as an order of magnitude in their estimates of the total areal extent of the Earth’s urban land (from 0.27 to 3.52 million km²). A sub-national analysis of the spatial distribution of urban land reveals that inter-map correlations are highest in North America ( $ \ifmmode\expandafter\bar\else\expandafter\=\fi{r} $  = 0.90), intermediate in Europe, South and Central America, and Sub-Saharan Africa ( $ \ifmmode\expandafter\bar\else\expandafter\=\fi{r} $  = 0.78), and lowest in Asia ( $ \ifmmode\expandafter\bar\else\expandafter\=\fi{r} $  = 0.63). Across most regions, our analysis uncovers a degree of variance that is high enough to call into question the consistency of each group’s approach to urban land, pointing to the need for both a common urban taxonomy and a global urban assessment effort.     

Structure and chemistry of (111) twin boundaries in MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel crystals from Mogok

The atomic scale structure and chemistry of (111) twins in MgAl₂O₄ spinel crystals from the Pinpyit locality near Mogok (Myanmar, formerly Burma) were analysed using complementary methods of transmission electron microscopy (TEM). To obtain a three-dimensional information on the atomic structure, the twin boundaries were investigated in crystallographic projections and Using conventional electron diffraction and high-resolution TEM (HRTEM) analysis we have shown that (111) twins in spinel can be crystallographically described by 180° rotation of the oxygen sublattice normal to the twin composition plane. This operation generates a local hcp stacking in otherwise ccp lattice and maintains a regular sequence of kagome and mixed layers. In addition to rotation, no other translations are present in (111) twins in these spinel crystals. Chemical analysis of the twin boundary was performed by energy-dispersive X-ray spectroscopy (EDS) using a variable beam diameter (VBD) technique, which is perfectly suited for analysing chemical composition of twin boundaries on a sub-nm scale. The VBD/EDS measurements indicated that (111) twin boundary in spinel is Mg-deficient. Quantitative analyses of HRTEM (phase contrast) and HAADF-STEM (Z-contrast) images of (111) twin boundary have confirmed that Mg²⁺ ions are replaced with Be²⁺ ions in boundary tetrahedral sites. The Be-rich twin boundary structure is closely related to BeAl₂O₄ (chrysoberyl) and BeMg₃Al₈O₁₆ (taaffeite) group of intermediate polysomatic minerals. Based on these results, we conclude that the formation of (111) twins in spinel is a preparatory stage of polytype/polysome formation (taaffeite) and is a result of thermodynamically favourable formation of hcp stacking due to Be incorporation on the {111} planes of the spinel structure in the nucleation stage of crystal growth. The twin structure grows as long as the surrounding geochemical conditions allow its formation. The incorporation of Be induces a 2D-anisotropy and exaggerated growth of the crystal along the (111) twin boundary.     

Transmission electron microscopy on iron monosulfide varieties from the Suizhou meteorite

Transmission electron microscopy on the iron monosulfide (FeS) varieties from the Suizhou meteorite (Hubei, China) reveals the intergrowth of primary hexagonal 2C troilite and minor monoclinic 4C pyrrhotite (SG: F2/d) phases as nanometer-scale domain microstructure. In addition, anti-phase domain boundaries are found to present in the 2C troilite superstructure with the displacement vector 1/4[001]_2C, which is expected to form during the translational symmetry breaking during cooling from higher symmetry, high-temperature modification of the NiAs-type (SG: P6₃/mmc) structure. Furthermore, 60° rotation twinning about the pseudo-hexagonal c-axis is observed in the 4C pyrrhotite superstructure, which may result from rotation symmetry reduction induced by the ordered arrangements of metal vacancies through solid-state transformation during further cooling. All the above microstructural characteristics are discussed with consideration to the thermal metamorphism history experienced by the Suizhou meteorite.     

Triclinic elastic constants for low albite

The full set of elastic constants for plagioclase end-member phase albite (NaAlSi₃O₈) is reported for the first time. Velocities of surface acoustic waves (both Rayleigh and pseudo-surface waves) were measured using impulsively stimulated light scattering on polished surfaces having six different orientations (three normal to the Cartesian axes and three lying on diagonals). Data were inverted and results tested using several non-linear optimization techniques. Compliance moduli determined under hydrostatic compression provided additional constraints and reduced covariance in the reported constants. The Cartesian coordinate system associated with the constants (using the unit cell) has the y-axis parallel to the crystal b axis, the x-axis parallel to a* (perpendicular to b and c) and the z-axis consistent with a right-handed coordinate system. The values of the moduli C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₂₂, C₂₃, C₂₄, C₂₅, C₂₆, C₃₃, C₃₄, C₃₅, C₃₆, C₄₄, C₄₅, C₄₆, C₅₅, C₅₆, C₆₆ and their 2σ uncertainties (in parentheses) are, respectively, 69.1(0.6), 34.0(0.7), 30.8(0.5), 5.1(0.1), −2.4(0.1), −0.9(0.1), 183.5(2.7), 5.5(2.2), −3.9(0.5), −7.7(0.7), −5.8(0.7), 179.5(2.3), −8.7(0.4), 7.1(0.6), −9.8(0.6), 24.9(0.1), −2.4(0.1), −7.2(0.1), 26.8 (0.2), 0.5(0.1), 33.5(0.2). These constants differ significantly from the previously reported pseudo-monoclinic constants that were based on velocity measurements on polysynthetic twinned crystal aggregates. Differences are consistent with systematic errors in the earlier study associated with sparse data and the presence of cracks and other imperfections.     

A powder neutron diffraction study of the crystal structure of the fluoroperovskite NaMgF<Subscript>3</Subscript> (neighborite) from 300 to 3.6 K

The cell dimensions and crystal structures of the fluoroperovskite NaMgF₃ (neighborite), synthesized by solid state methods, have been determined by powder neutron diffraction and Rietveld refinement over the temperature range 300–3.6 K using Pt metal as an internal standard for calibration of the neutron wavelength. These data show that Pbnm NaMgF₃ does not undergo any phase transitions to structures of lower symmetry with decreasing temperature. The cell dimensions and atomic coordinates together with polyhedron volumes and distortion indices are given for Pbnm NaMgF₃ at 25 K intervals from 300 to 3.6 K. Decreases in the a and c cell dimensions reach a saturation point at 50 K, whereas the b dimension becomes saturated at 150 K. The distortion of the structure of Pbnm NaMgF₃ from the aristotype cubic structure is described in terms of the tilting of the MgF₆ octahedra according to the tilt scheme a ⁻ a ⁻ c ⁺ . With decreasing temperature the antiphase tilt (a ⁻) increases from 14.24° to 15.39°, whereas the in-phase tilt (c ⁺ ) remains effectively constant at ∼10.7°. Changes in the tilt angles are insufficient to cause changes in the coordination sphere of Na that might induce a low temperature phase transition. The structure of Pbnm NaMgF₃ is also described in terms of normal mode analysis and displacements of the condensed normal modes are compared with those of Pbnm KCaF₃.     

Germanium-bearing Colusite in Siliceous Black Ore from the Ezuri Kuroko Deposit, Hokuroku District, Japan

Abstract. Germanium‐bearing colusite occurs with sphalerite, galena, tetrahedrite‐tennantite, chalcopyrite and pyrite in microdruses and veinlets in the siliceous black ore from the Ezuri Kuroko deposit in the Hokuroku district of Japan. X‐ray microdiffractometry of this mineral gives strongest lines at 1.60, 1.32 and 1.09 Å, which are consistent with the known powder diffraction data of colusite. On the basis of 32 S atoms per formula unit, electron microprobe analyses yield empirical chemical formulae of (Cu_{24 0}Fe_0.3Zn_1.0)_σ25.3V_1.9(A_s4.8Sb_0.2)_σ5.0Ge _1.3S₃₂ for Ge‐bearing colusite in close association with sphalerite, and (Cu_24.6Fe_0.9)_σ25.4V_1.8(A_s4.1 Sb_0.2)_σ4.3Ge_1.7S₃₂ for that coexisting with chalcopyrite, consistent with the ideal formula of Cu_24+xV₂(As, Sb)_6‐x(Sn, Ge)_xS₃₂ (x = 0 to 2) proposed by Spry et al. (1994) for this mineral species. The Ge‐bearing colusite mineralization is suggested to have occurred concurrently with consolidation of the siliceous black ore, possibly during hydrothermal modification in association with the igneous activity of the Ohtaki quartz diorite of the later Onnagawa stage. It is likely that biogenic siliceous ooze, a possible precursor of the siliceous black ore, may have served as an in situ source of Ge as well as other essential rare elements, leading to the formation of Ge‐bearing colusite during transformation or recrystallization of biogenic opal into a‐quartz.     

Potential protonation sites in the Al<Subscript>2</Subscript>SiO<Subscript>5</Subscript> polymorphs based on polarized FTIR spectroscopy and properties of the electron density distribution

Potential protonation sites for, kyanite, sillimanite, and andalusite, located in a mapping of the (3, −3) critical points displayed by their L(r) = −∇²ρ(r) distributions, are compared with polarized single-crystal FTIR spectra of kyanite and sillimanite determined earlier and with andalusite measured in this study. For andalusite, seven peaks were observed when the electric vector, E, is parallel to [100]: four intense ones at 3,440, 3,460, 3,526, and 3,597 cm⁻¹ and three weaker ones at 3,480, 3,520, and 3,653 cm⁻¹. Six peaks, three intense ones at 3,440, 3,460, and 3,526 cm⁻¹ and three weaker ones at 3,480, 3,520, and 3,653 cm⁻¹ when E parallels [010]. No peaks were observed when E is parallel to [001]. The concentration of water in andalusite varies between 110 and 168 ppm by weight % H₂O. Polarized FTIR spectra indicate that the OH vector is parallel to (001) in andalusite and sillimanite and in kyanite. Examination of the L(r) (3, −3) critical points in comparison with the polarized FTIR indicates that H prefers to bond to the oxygen atoms O1 and O2 in andalusite and O2 and O4 in sillimanite which correspond to the underbonded oxygen atoms and those with the largest L(r) maxima. In kyanite, comparison of the FTIR spectrum and the critical points indicates that H will preferentially bond to the two 4-coordinated O2 and O6 atoms.     

Rare minerals from Rajpura-Dariba,Rajasthan, India. VII: Renierite

Summary The first Indian occurrence of renierite, [Cu₁₀(Cu_0.09Zn_0.71Fe_0.15)_0.15Fe₄(Ge_1.68V_0.03-As_0.27)_1.98]_16.93S_16.08 is reported from the Cu-rich basal zone of the polymetallic deposit at Rajpura-Dariba. Optical, X-ray and electron microprobe data on the mineral are compared with those from other occurrences. A slight excess of the iron content compared with the formula Cu₁₀(Zn_1–x Cu _x )(Ge_2–x As _x )Fe₄S₁₆ ofBernstein (1986) and noticeable differences between Cu-coefficient (in brackets) and As-coefficient are obtained. The substitution scheme in renierite may be more complicated than that suggested byBernstein (1986), and apparently also includes the substitution Cu Zn Fe together with As Ge.

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Seltene Minerale von Rajpura-Dariba, India. VII: Renierit

Zusammenfassung Das erste indische Vorkommen von Renierit [Cu₁₀(Cu_0.09Zn_0.71Fe_0.15)_0.15Fe₄(Ge_1.68V_0.03As_0.27)_1.98]_16.93S_16.08 wird mitgeteilt; dieses liegt in der Kupfer-reichen liegenden Zone der polymetallischen Lagerstätte von Rajpura-Dariba. Optische, Röntgen- und Mikrosondendaten dieses Minerals werden mit solchen von anderen Vorkommen verglichen. Ein leichter Überschuß des Eisengehaltes verglichen mit der Formel Cu₁₀(Zn_1–x Cu _x )(Ge_2–x As _x )Fe₄S₁₆ vonBernstein (1986) und Unterschiede zwischen dem Cu-Koeffizient (in Klammer) und dem As-Koeffizient wurden festgestellt. Die Art der Substitution in Renierit dürfte komplizierter sein als vonBernstein (1986) vorgeschlagen. Die Substitution Cu Zn Fe zusammen mit As scheint hier eine Rolle zu spielen.

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With 4 Figures     

Crystal structures of iron bearing tetrahedrite and tennantite at 25 and 250°C by means of Rietveld refinement of synchrotron data

Rietveld refinement of X-ray synchrotron data was performed for two synthetic tetrahedrite samples, with 0.61 and 1.83 Fe atoms, and two synthetic tennantite samples with 0.10 and 1.23 Fe atoms p.f.u. M₁₂(Sb,As)₄S₁₃. Measurements were performed at 25 and 250°C. For both the phases, increased Fe substitution is reflected in the increased tetrahedral ‘Cu1’–S distance (‘Cu1’ is a site of Fe substitution) and Cu2–S distances. Cu2 was refined as a split position; the Cu2–Cu2 split about the plane of the S1₂S2 triangle is about 0.56 and 0.65 Å for tetrahedrite and tennantite, respectively. Cu2–Cu2 distances in the structure cavity are 2.8–2.9 Å. Between 25 and 250°C, the lattice parameter a increased by 0.02–0.04 Å and the interatomic distances by 0.01 Å on an average. Thermal expansion coefficients of little-substituted samples are similar to those of unsubstituted samples, whereas thermal expansion appears to decrease with increasing substitution by Fe. The Cu2–Cu2 split increases at 250°C by about 0.1 Å for tetrahedrite and by more than 0.15 Å for tennantite but the cage expansion is minimal so that the Cu2–Cu2 distances in the cavity decrease with temperature. Difference Fourier maps indicate that there is little residual electron density left between the two Cu2 half-sites in tetrahedrite but this inter-site density is substantially higher in tennantite. It increases with temperature, especially in the little-substituted tennantite sample.     

Fe-Zn exchange reaction between tetrahedrite and sphalerite in natural environments

Microprobe and fluid inclusion analyses of hydrothermal ore deposits containing the subassemblage sphalerite+ tetrahedrite-tennantite [(Cu, Ag)₁₀(Fe, Zn)₂(As,Sb)₄S₁₃] reveal that the Gibbs energies of the reciprocal reaction Cu₁₀Zn₂Sb₄S₁₃ + Cu₁₀Fe₂As₄S₁₃ = Cu₁₀Fe₂Sb₄S₁₃ + Cu₁₀Zn₂As₄S₁₃ and the Fe-Zn exchange reaction 1/2Cu₁₀Fe₂Sb₄S₁₃ + ZnS = 1/2Cu₁₀Zn₂Sb₄S₁₃ + FeS are within the uncertainties of the values established by Sack and Loucks (1985) and Raabe and Sack (1984), 2.59±0.14 and 2.07±0.07 kcal/gfw. However, this study suggests that the Fe-Zn exchange reaction between sphalerite and Sb and Ag-rich tetrahedrites does not obey the simple systematics suggested by Sack and Loucks (1985) wherein tetrahedrite is assumed to behave as an ideal reciprocal solution. Instead these studies show that the configurational Gibbs energy of this exchange reaction,RTln[(X _Fe/X _Zn)^TET(X _ZnS/X _FeS)^SPH], corrected for sphalerite nonideality exhibits both a local maximum and minimum as a function of Ag/(Cu+Ag) ratio at a givenX _FeS ^SPH and temperature. The local maximum forX _FeS ^SPH 0.10 corresponds to the position of the cell edge maximum established for natural tetrahedrites by Riley (1974), Ag/(Ag+Cu)0.4. These studies and the results of structural refinements of Ag-bearing tetrahedrites suggest that in low silver tetrahedrites Ag is preferentially incorporated in trigonal-planar sites but that in tetrahedrites with intermediate and greater Ag/(Ag+Cu) ratio, Ag is preferentially incorporated in tetrahedral sites. A nonconvergent site ordering model for tetrahedrite is developed to quantify and extrapolate these predictions.     

A new Cu-rich variety of lyonsite from fumarolic sublimates of the Tolbachik volcano (Kamchatka, Russia) and its crystal structure

A new Cu-rich variety of lyonsite has been found from fumarolic sublimates of the Tolbachik volcano (Kamchatka, Russia). The empirical formula is Cu_4.33Fe _2.37 ³⁺ Ti_0.26Al_0.26Zn_0.07(V_5.85As_0.07Mo_0.07P_0.01S_0.01)O₂₄. The crystal structure was studied on single crystal using synchrotron radiation, R = 0.0514. The mineral is orthorhombic, Pnma, a = 5.1736(7), b =10.8929(12), c = 18.220(2) Å, V = 1026.8(2) ų, and Z = 2. The structural formula is (Cu_0.6Ti_0.3Al_0.3Fe _0.2 ³⁺ □_0.6)_Σ2Cu₂(Fe _2.2 ³⁺ Cu_1.8)_Σ4(V_5.8As_0.1Mo_0.1)_Σ6O₂₄. It is proposed to recast the simplified formula of lyonsite as Cu_3+x (Fe _4?2x ³⁺ Cu_2x )(VO₄)₆, where 0 ≤ x ≤ 1.     

The role of Fe2+ and Fe3+ in synthetic Fe-substituted tetrahedrite

Summary Tetrahedrites with the composition between Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ were synthesized at 457 °C and 500 °C from the elements and carefully studied by Mössbauer spectroscopy of⁵⁷Fe. Between Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ iron is predominantly ferric. Between Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ iron is predominantly ferrous and occupies the tetrahedral M1-sites.

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Zusammenfassung Die Rolle von Fe²⁺ und Fe³⁺ in synthetischen Tetraedriten mit Fe-Substitution Tetraedrite mit einer Zusammensetzung zwischen Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ wurden bei 457 °C und 500 °C aus den Elementen synthetisiert und sorgfdltig mit Mössbauer-Spektroskopie von⁵⁷Fe untersucht. Zwischen Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ ist Eisen überwiegend dreiwertig. Zwischen Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₁Fe₂Sb₄S₁₃ ist Eisen überwiegend zweiwertig und besetzt die tetraedrisch koordinierten M1-Plätze.

     

The system Pb-As-S

Silica-tube quenching experiments and gold-tube pressure experiments were used to study phase relations in the PbS-rich portion of the system Pb-As-S. Emphasis was placed on determining the P-T-X stability relations of jordanite, the most Pb-rich of the synthetic Pb-As-S compounds. Jordanite, Pb₉As₄S₁₅, is stable below 549 ± 3° C, at which temperature it melts to galena, liquid, and a sulfur-rich vapor phase. Confining pressures of up to 2 Kb do not measurably change this reaction temperature. Density measurements on synthetic material show that the jordanite cell contains 3 (Pb₉As₄S₁₅); space group P2₁/m requires that the cell content be expressed as either Pb_28–xAs₁₂S_46–x or Pb_26+xAs₁₂S_44+x, with the former much more probable from a structural point of view. In both cases 0.8 < x < 1.4 and the situation is thus quite different from the usual case of defect structures, such as pyrrhotite, Fe_1–xS, which shows considerable range of solid solution. Heating experiments on natural gratonite (Pb₉As₄S₁₅) show that this mineral is most probably a low-temperature dimorph of jordanite, the inversion occurring below 250° C. Experiments have also confirmed the extensive substitution of Sb for As in jordanite, as suspected from chemical analyses of the isostructural mineral geocronite (Pb_28–x(As,Sb)₁₂S_46–x).

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Zusammenfassung Durch Abschreckversuche mit Hilfe von Quarz- und Gold-Druckampullen wurden die Phasenbeziehungen im PbS-reichen Teil des Pb-As-S-Systems studiert. Besonderer Wert wurde auf die Feststellung der P-T-X-Stabilitätsverhältnisse des Jordanits, des Pb-reichsten Phase der synthetischen Pb-As-S-Reihe, gelegt. Jordanit (Pb₉As₄S₁₅) ist unterhalb 549 ± 3° C stabil, wo er sich semikongruent zu PbS, einer Schmelze und einer schwefelreichen Dampfphase zersetzt. Drucke bis zu 2 kb ergaben keine meßbaren Änderungen dieser Reaktionstemperatur. Dichtemessungen am synthetischen Material weisen darauf hin, daß die Jordanitzelle 3 × (Pb₉As₄S₁₅) enthält. Die Raumgruppe P2₁/m fordert entweder die Formel Pb_28–xAs₁₂S_46–x oder Pb_26+xAs₁₂S_44+x, wobei die erstere Form strukturell wahrscheinlicher zu sein scheint. In beiden Fällen ist 0.8 < x < 1.4 und weicht vom gebräuchlichen Begriff der Defektstrukturen, wie z.B. beim Pyrrhotin (Fe_1–xS) ab, wie das bemerkenswerte Mischkristallfeld zeigt. Erhitzen von natürlichem Gratonit (Pb₉As₄S₁₅) zeigt, daß dieses Mineral sehr wahrscheinlich eine dimorphe Tieftemperaturphase des Jordanits ist. Die Umwandlung erfolgt unterhalb 250° C. Außerdem wurde eine umfangreichere Substitution von As durch Sb im Jordanit festgestellt, was nach den chemischen Analysen des isostrukturellen Geochronits Pb_28–x(As,Sb)₁₂S_46–x) zu erwarten war.

     

Influence of hydrogen on Fe–Mg interdiffusion in (Mg,Fe)O and implications for Earth’s lower mantle

Interdiffusion of Fe and Mg in (Mg,Fe)O has been investigated experimentally under hydrous conditions. Single crystals of MgO in contact with (Mg_0.73Fe_0.27)O were annealed hydrothermally at 300 MPa between 1,000 and 1,250°C and using a Ni–NiO buffer. After electron microprobe analyses, the dependence of the interdiffusivity on Fe concentration was determined using a Boltzmann–Matano analysis. For a water fugacity of ∼300 MPa, the Fe–Mg interdiffusion coefficient in Fe _x Mg_1−x O with 0.01 ≤ x ≤ 0.25 can be described by with and C = −80 ± 10 kJ mol⁻¹. For x = 0.1 and at 1,000°C, Fe–Mg interdiffusion is a factor of ∼4 faster under hydrous than under anhydrous conditions. This enhanced rate of interdiffusion is attributed to an increased concentration of metal vacancies resulting from the incorporation of hydrogen. Such water-induced enhancement of kinetics may have important implications for the rheological properties of the lower mantle.

Oxidation modes and thermodynamics of Fe oxyhydroxycarbonate green rust: Dissolution-precipitation versus in situ deprotonation

Fe^II-III hydroxycarbonate green rust GR(CO₃²⁻), Fe^II₄ Fe^III₂ (OH)₁₂ CO₃·3H₂O, is oxidized in aqueous solutions with varying reaction kinetics. Rapid oxidation with either H₂O₂ or dissolved oxygen under neutral and alkaline conditions leads to the formation of ferric oxyhydroxycarbonate GR(CO₃²⁻)∗, Fe^III₆ O₁₂ H₈ CO₃·3H₂O, via a solid-state reaction. By decreasing the flow of oxygen bubbled in the solution, goethite α-FeOOH forms by dissolution-precipitation mechanism whereas a mixture of non-stoichiometric magnetite Fe_(3−x)O₄ and goethite is observed for lower oxidation rates. The intermediate Fe^II-III oxyhydroxycarbonate of formula Fe^II_6(1−x) Fe^III_6x O₁₂ H_2(7−3x) CO₃·3H₂O, i.e. GR(x)∗ for which x ? [1/3, 1], is the synthetic compound that is homologous to the fougerite mineral present in hydromorphic gleysol; in situ oxidation accounts for the variation of ferric molar fraction x = [Fe^III]/{[Fe^II]+[Fe^III]} observed in the field as a function of depth and season but limited to the range [1/3, 2/3]. The domain of stability for partially oxidized green rust is observed in the E_h-pH Pourbaix diagrams if thermodynamic properties of GR(x)∗ is compared with those of lepidocrocite, γ-FeOOH, and goethite, α-FeOOH. Electrochemical equilibrium between GR(x)∗ and Fe^II in solution corresponds to E_h-pH conditions close to those measured in the field. Therefore, the reductive dissolution of GR(x)∗ can explain the relatively large concentration of Fe^II measured in aqueous medium of hydromorphic soils containing fougerite.     

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     

Mineralogy and genetic features of the Cu-As-Ni-Sb-Pb mineralization from the Mlakva polymetallic deposit (Serbia) — New occurrence of (Ni-Sb)-bearing Cu-arsenides

(Ni-Sb)-bearing Cu-arsenides are rare minerals within the Mlakva and Kram mining sectors (Boranja ore field) one of the less-known Serbian Cu deposits. (Ni-Sb)-bearing Cu-arsenides were collected from the Mlakva skarn-replacement Cu(Ag,Bi)-FeS polymetallic deposit. The identified phases include β-domeykite, Ni-bearing koutekite and (Ni-Sb)-bearing α-domeykite. (Ni-Sb)-bearing Cu-arsenides are associated with nickeline, arsenical breithauptite, chalcocite, native Ag, native Pb and litharge. Pyrrhotite, pyrite, chalcopyrite, cubanite, bismuthinite, molybdenite, sphalerite, galena, Pb(Cu)-Bi sulfosalts and native Bi, as well as minor magnetite, scheelite and powellite are associated with the sulfide paragenesis. The electron microprobe analyses of the (Ni-Sb)-bearing Cu-arsenides yielded the following average formulae: (Cu_2.73,Ni_0.17,Fe_0.03,Ag_0.01)_∑ 2.94(As_0.98,Sb_0.05,S_0.02)_∑ 1.06–β-domeykite (simplified formula (Cu_2.7,Ni_0.2)_∑ 2.9As_1.1); (Cu_3.40,Ni_1.40,Fe_0.11)_∑ 4.91(As_1.94,Sb_0.13,S_0.02)_∑ 2.08–Ni-bearing koutekite (simplified formula (Cu_3.4Ni_1.5)_∑ 4.9As_2.1); and Cu_1.97(Ni_0.98,Fe_0.03)_∑ 1.01(As_0.81,Sb_0.22)_∑ 1.03–(Ni–Sb)-bearing α-domeykite (simplified formula Cu₂NiAs). The Rietveld refinement yielded the following unit-cell parameters for β-domeykite and Ni–bearing koutekite: a = 7.1331(4); c = 7.3042(5) Å; V = 321.86(2) ų, and a = 5.922(4); b = 11.447(9); c = 5.480(4) Å; V = 371.48(5) ų, respectively. Ore geology, paragenetic assemblages and genesis of the Mlakva deposit are discussed in detail and the Cu-As-Ni-Sb-Pb mineralization has been compared with similar well-known global deposits.     

Oxidation state and electronic configuration determination of copper in tetrahedrite group minerals by L-edge X-ray absorption spectroscopy

L-edge X-ray absorption spectroscopy employing a synchrotron radiation source has been used to study the electronic structure and valency of Cu in the chemically and structurally complex tetrahedrite group of minerals. Mechanical mixtures of Cu²⁺O and Cu⁺FeS₂ were used to estimate the relative cross sections of Cu²⁺ and Cu⁺; the absorption of Cu²⁺ at 931 eV is 25 times greater than that of Cu⁺ at 945 eV. Using this calibration, Cu²⁺/Cu ratios were found to vary from 0.00 to 0.054 in the tetrahedrite samples studied; the highest proportion of Cu²⁺ occurs in synthetic tetrahedrites with a composition close to Cu₁₂Sb₄S₁₃. This study reveals the utility of the technique for determining the valence state of copper in complex minerals, allowing the crystal chemistry to be more fully characterised.     

Kinetics of Fe<Superscript>2+</Superscript>–Mg order–disorder in orthopyroxene: experimental studies and applications to cooling rates of rocks

We determined the forward rate constant (K⁺) for the Fe²⁺–Mg order–disorder between the M2 and M1 sites of orthopyroxene (OPx), which is described by the homogeneous reaction Fe²⁺ (M2) + Mg(M1) ↔ Mg(M2) + Fe²⁺ (M1), by both ordering and disordering experiments at isothermal condition and also by continuous cooling experiments. The rate constant was determined as a function of temperature in the range of 550–750°C, oxygen fugacity between quartz–fayalite–iron and Ni–NiO buffers, and at compositions of 16 and 50 mol% ferrosilite component. The K⁺ value derived from disordering experiment was found to be larger than that derived from ordering experiment at 550°C, while at T>580°C, these two values are essentially the same. The fO₂ dependence of the rate constant can be described by the relation K⁺ α (fO₂) ⁿ with n=5.5–6.5, which is compatible with the theoretically expected relation. The Arrhenius relation at the WI buffer condition is given by