An X-ray photoelectron and absorption spectroscopic investigation of the electronic structure of cubanite, CuFe2S3

X-ray photoelectron and absorption spectra have been obtained for natural specimens of cubanite and compared with the corresponding spectra for chalcopyrite. Synchrotron X-ray photoelectron spectra of surfaces prepared by fracture under ultra-high vacuum revealed some clear differences for the two minerals, most notably those reflecting their different structures. In particular, the concentration of the low binding energy S species formed at cubanite fracture surfaces was approximately double that produced at chalcopyrite surfaces. However, the core electron binding energies for the two S environments in cubanite were not significantly different, and were similar to the corresponding values for the single environment in chalcopyrite. High binding energy features in the S 2p and Cu 2p spectra were not related to surface species produced either by the fracture or by oxidation, and most probably arose from energy loss due to inter-band excitation. Differences relating to the Fe electronic environments were detectable, but were smaller than expected from some of the observed physical properties and Mössbauer spectroscopic parameters for the two minerals. X-ray absorption and photoelectron spectra together with the calculated densities of states for cubanite confirmed an oxidation state of Cu^I in the mineral. It was concluded that the best formal oxidation state representation for cubanite is Cu^I(Fe₂)^VS ₃ ^?II .     

Composition features of isocubanite and polymorphous modifications of CuFe2S3 compound

The results of studying isocubanite from sulfide ores of recent oceanic black smokers and sulfide mud of the Red Sea are compared with those of isocubanite from ores of the Noril’sk ore field and isocubanite synthesized in the course of experimental study of the Cu–Fe–S system. Isocubanite associated with chalcopyrite is enriched in Cu, whereas that associated with pyrrhotite or with pyrrhotite and haycockite is enriched in Fe. According to data in the literature, the CuFe₂S₃ compound has four polymorphous modifications: orthorhombic cubanite, tetragonal, hexagonal, and cubic isocubanite. Cubanite, and tetragonal and hexagonal modifications of the CuFe₂S₃ compound are high-pressure minerals. Therefore, they may be used as barometers.     

High-pressure polymorphism and structural transitions of norsethite,BaMg(CO3)2

In situ high-pressure investigations on norsethite, BaMg(CO₃)₂, have been performed in sequence of diamond-anvil cell experiments by means of single-crystal X-ray and synchrotron diffraction and Raman spectroscopy. Isothermal hydrostatic compression at room temperature yields a high-pressure phase transition at P _c ≈ 2.32 ± 0.04 GPa, which is weakly first order in character and reveals significant elastic softening of the high-pressure form of norsethite. X-ray structure determination reveals C2/c symmetry (Z = 4; a = 8.6522(14) Å, b = 4.9774(13) Å, c = 11.1542(9) Å, β = 104.928(8)°, V = 464.20(12) Å³ at 3.00 GPa), and the structure refinement (R ₁ = 0.0763) confirms a distorted, but topologically similar crystal structure of the so-called γ-norsethite, with Ba in 12-fold and Mg in octahedral coordination. The CO₃ groups were found to get tilted off the ab-plane direction by ~16.5°. Positional shifts, in particular of the Ba atoms and the three crystallographically independent oxygen sites, give a higher flexibility for atomic displacements, from which both the relatively higher compressibility and the remarkable softening originate. The corresponding bulk moduli are K ₀ = 66.2 ± 2.3 GPa and dK/dP = 2.0 ± 1.8 for α-norsethite and K ₀ = 41.9 ± 0.4 GPa and dK/dP = 6.1 ± 0.3 for γ-norsethite, displaying a pronounced directional anisotropy (α: β _a ^?1  = 444(53) GPa, β _c ^?1  = 76(2) GPa; γ: β _a ^?1  = 5.1(1.3) × 10³ GPa, β _b ^?1  = 193(6) GPa β _c ^?1  = 53.4(0.4) GPa). High-pressure Raman spectra show a significant splitting of several modes, which were used to identify the transformation in high-pressure high-temperature experiments in the range up to 4 GPa and 542 K. Based on the experimental series of data points determined by XRD and Raman measurements, the phase boundary of the α-to-γ-transition was determined with a Clausius–Clapeyron slope of 9.8(7) × 10^?3 GPa K^?1. An in situ measurement of the X-ray intensities was taken at 1.5 GPa and 411 K in order to identify the nature of the structural variation on increased temperatures corresponding to the previously reported transformation from α- to β-norsethite at 343 K and 1 bar. The investigations revealed, in contrast to all X-ray diffraction data recorded at 298 K, the disappearance of the superstructure reflections and the observed reflection conditions confirm the anticipated \(R\bar{3}m\) space-group symmetry. The same superstructure reflections, which disappear as temperature increases, were found to gain in intensity due to the positional shift of the Ba atoms in the γ-phase.     

High-pressure crystal chemistry of phenakite (Be2SiO4) and bertrandite (Be4Si2O7(OH)2)

Compressibilities and high-pressure crystal structures have been determined by X-ray methods at several pressures for phenakite and bertrandite. Phenakite (hexagonal, space group R \(\bar 3\) ) has nearly isotropic compressibility with β=1.60±0.03×10^?4 kbar^?1 and β=1.45±0.07×10^?4 kbar^?1. The bulk modulus and its pressure derivative, based on a second-order Birch-Murnaghan equation of state, are 2.01±0.08 Mbar and 2±4, respectively. Bertrandite (orthorhombic, space group Cmc2₁) has anisotropic compression, with β _a =3.61±0.08, β _b =5.78±0.13 and β _c =3.19±0.01 (all ×10^?4 kbar^?1). The bulk modulus and its pressure derivative are calculated to be 0.70±0.03 Mbar and 5.3±1.5, respectively. Both minerals are composed of frameworks of beryllium and silicon tetrahedra, all of which have tetrahedral bulk moduli of approximately 2 Mbar. The significant differences in linear compressibilities of the two structures are a consequence of different degrees of T-O-T bending.     

High-pressure investigations on the isostructural phase transition and metallization in realgar with diamond anvil cells

The high-pressure structural,vibrational and electrical properties for realgar were investigated by in-situ Raman scattering and electrical conductivity experiments combined with first-principle calculations up to~30.8 GPa.It was verified that realgar underwent an isostructural phase transition at~6.3 GPa and a metallization at a higher pressure of~23.5 GPa.The isostructural phase transition was well evidenced by the obvious variations of Raman peaks,electrical conductivity,crystal parameters and the As–S bond length.The phase transition of metallization was in closely associated with the closure of bandgap rather than caused by the structural phase transition.And furthermore,the metallic realgar exhibited a relatively low compressibility with the unit cell volume V₀=718.1.4?³and bulk modulus B₀=36.1 GPa.     

High-pressure phase transformation of carbonate malachite Cu2(CO3)(OH)2 driven by [CuO6] regularization and [CO3] rotation

High-pressure synchrotron X-ray diffraction and infrared absorption spectroscopy have been employed to study the crystal chemistry and phase transitions in an[OH]-bearing carbonate,malachite Cu2(CO₃)(OH)₂,to determine the effect of[OH]on the stability of carbonate.We found that the crystal structure of malachite is stabilized by a high degree of[CuO₆]-octahedron distortion,as is manifested by large variations in Cu–O bond lengths resulting from oxygen atoms that connect to hydrogen at crystallographically different sites.External pressure offsets the effect of hydrogen bond,promotes[CuO₆]compression and regularization and accordingly[CO₃]rotation.Rotation of[CO₃]-triangles,in turn,assists in a conversion in the crystal orientation of the[CuO₆]structural unit.During compression to above~6 GPa,malachite begins to turn into the rosasite lattice,accompanied with a jump in density of 3.3%.Rosasite is characterized with a hardened lattice and preserves to the maximum pressure(18.2 GPa)of the present study.Phase transformation mechanism of malachite to rosasite is different from that of carbonates,with the latter being driven by an almost uniform compression of[MO₆]-octahedron(M=Ca,Cd,Mn,Fe,Zn,Mg,etc.)and rotation/translation of[CO₃]-triangle under pressure.     

离子色谱法测定水样中S2-、SO2-3、SO2-4、S2O2-3

该种方法利用离子色谱仪的电导检测器与电化学检测器串联,十几分钟即可连续完成水中S2-、SO2-3、SO2-4、S2O2-3的测定,方法具有快速、高效、方便、灵敏、选择性好等特点.方法的检出限分别为S2-12.5μg/L;SO2-3 22.4μg/L;SO2-4 5.0μg/L;S2O2-3 5.0μg/L.相对标准偏差在1.5%～6.9%之间,能够满足水中S2-、SO2-3、SO2-4、S2O2-3四种阴离子分析测试的需要.     

非线性成矿预测理论:多重分形奇异性-广义自相似性-分形谱系模型与方法

介绍了“奇异性-广义自相似性-分形谱系”(“3S”: Singularity-generalized self-Similarity-fractal Spectrum)为核心的多重分形现代成矿预测理论与模型(Multifractal Mineralization Prediction Theory and Models)的基本内容和前沿研究方向.讨论了作为非线性、复杂性理论的重要领域之一, 多重分形理论所提供的“奇异性-广义自相似性-分形谱系”等概念和相关的模型.这些新概念和模型不仅能够合理地描述成矿系统、成矿过程、成矿富集规律、矿产资源时空分布, 还提供了定量模拟和识别成矿异常(地质、地球物理、地球化学、遥感异常)的有效模型和实用方法.将多重分形原理与成矿过程、矿产资源分布规律、矿产资源信息获取研究相结合, 可形成具有良好应用前景的现代成矿预测理论与模型.采用该多重分形矿产资源预测理论和在此基础上所开发的专用地学非线性空间信息GeoDASGIS技术, 对国内外多个金属成矿区带进行了矿产资源勘查与评价, 均取得了较理想的预测效果, 表明对开展矿产资源勘查和评价是有效和可行的.      

High-pressure phase transformations in the MgFe2O4 and Fe2O3–MgSiO3 systems

 The crystal structure of MgFe₂O₄ was investigated by in situ X-ray diffraction at high pressure, using YAG laser annealing in a diamond anvil cell. Magnesioferrite undergoes a phase transformation at about 25 GPa, which leads to a CaMn₂O₄-type polymorph about 8% denser, as determined using Rietveld analysis. The consequences of the occurrence of this dense MgFe₂O₄ form on the high-pressure phase transformations in the (MgSi)_0.75(Fe^III)_0.5O₃ system were investigated. After laser annealing at about 20 GPa, we observe decomposition to two phases: stishovite and a spinel-derived structure with orthorhombic symmetry and probably intermediate composition between MgFe₂O₄ and Mg₂SiO₄. At pressures above 35 GPa, we observe recombination of these products to a single phase with Pbnm perovskite structure. We thus conclude for the formation of Mg₃Fe₂Si₃O₁₂ perovskite. Received: 27 March 2000 / Accepted: 1 October 2000     

High-pressure synthesis and properties of magnesiocarpholite,MgAl2[Si2O6] (OH)4

Magnesiocarpholite has been synthesized on its own composition between 15 and 25 kb water pressure and 415°–600° C. Best conditions are 25 kb-550° C, starting from a mixture of oxides and synthetic cordierite. Within the MgO-Al₂O₃-SiO₂-H₂O system, possible substitutions appear to be very limited in magnesiocarpholite. Cell-parameters are a=13.706(3), b= 20.075(3), c=5.107(l) Å, space group Ccca. The larger cell, as compared with the most magnesian natural carpholites, is tentatively ascribed to structural disorder. Preliminary stability data confirm the low-temperature character of this mineral which is shown to be a high-pressure equivalent of sudoite+quartz.     

滇西锡矿的花岗岩类及其成矿作用

滇西锡矿是三江锡矿域的主体。本文论述了三江锡矿域与东南亚锡矿域各带的对比,指出滇西锡矿受特提斯构造演化的控制。腾冲一梁河地区花岗岩类首次划出3个岩群、8个超单元、28个单元和若干侵入体。对滇西原生锡矿床类型、成矿系列和成矿特征进行了较详细的研究。     

High-pressure properties of diaspore,AlO(OH)

The structural compression mechanism and compressibility of diaspore, AlO(OH), were investigated by in situ single-crystal synchrotron X-ray diffraction at pressures up to 7 GPa using the diamond-anvil cell technique. Complementary density functional theory based model calculations at pressures up to 40 GPa revealed additional information on the pressure-dependence of the hydrogen-bond geometry and the vibrational properties of diaspore. A fit of a second-order Birch–Murnaghan equation of state to the p–V data resulted in the bulk modulus B ₀ = 150(3) GPa and B ₀ = 150.9(4) GPa for the experimental and theoretical data, respectively, while a fit of a third-order Birch–Murnaghan equation of state resulted in B ₀ = 143.7(9) GPa with its pressure derivative B′ = 4.4(6) for the theoretical data. The compression is anisotropic, with the a-axis being most compressible. The compression of the crystal structure proceeds mainly by bond shortening, and particularly by compression of the hydrogen bond, which crosses the channels of the crystal structure in the (001) plane, in a direction nearly parallel to the a-axis, and hence is responsible for the pronounced compression of this axis. While the hydrogen bond strength increases with pressure, a symmetrisation is not reached in the investigated pressure range up to 40 GPa and does not seem likely to occur in diaspore even at higher pressures. The stretching frequencies of the O–H bond decrease approximately linearly with increasing pressure, and therefore also with increasing O–H bond length and decreasing hydrogen bond length. Electronic Supplementary Material The online version of this article () contains supplementary material, which is available to authorized users.     

Phase relations in the systems Cu2S-PbS-Bi2S3 and Ag2S-PbS-Bi2S3 and their mineral assemblages

The phase diagrams of the systems Cu₂S-PbS-Bi₂S₃ and Ag₂S-PbS-Bi₂S₃ have been investigated in the present study. The paper is concerned with the complete solid solution between bismuthtite and aikinite above 300°C in the system Cu₂S-PbS-Bi₂S₃. The synthetic phases CuBi₃S₅ and Cu₃Bi₅S₉ have their solid solution ranges in the ternary system with 9 and 26 mole% PbS at maximum, respectively. A complete solid solution between PbS and AgBiS₂ divides the phase diagram of the system Ag₂S-PbS-Bi₂S₃ into two parts: Bi-rich and Ag-rich. All sulfosalt minerals and solid solutions, including pavonite ss, lillianite ss, heyovskyite and benjaminite are on the Bi-rich side. And divarant relations were found between pavonite ss -lillianite ss, benjaminite and bismuthtite as well as between lillianite ss -bismuthtite and galenobismutite. Synthetic experiments using LiCl-KCl flux technique show that when a minor amount of copper (less lwt.%) is added in, many of Ag-and Pb-bismuth sulfosalt minerals, for example, vikingite (Ag₅Pb₈Bi₁₃S₃₀), are synthesized successively, particularly at 400°C. So is heyrovskyite, which has a solid solution range with 3.7 mole% Cu₂S at maximum in the system Cu₂S-PbS-Bi₂S₃.     

Chemistry of some Pb-(Cu,Fe)-(Sb,Bi sulfosalts from France and Portugal. Implications for the crystal chemistry of lead sulfosalts in the Cu-poor part of the Pb2S2-Cu2S-Sb2S3-Bi2-Bi2S3 system

Electron microprobe analysis of Pb-Cu(Fe)-Sb-Bi sulfosalts from Bazoges and Les Chalanches (France), and Pedra Luz (Portugal), give new data about (Bi, Sb) solid-solution and incorporation of the minor elements Cu, Fe or Ag in jaskolskiite, and in izoklakeite-giessenite and kobellite-tintinaite series. Jaskolskiite from Pedra Luz has high Sb contents (from 17.9 to 20.7 wt.%), leading to the extended general formula: Cu _x Pb_2+x (Sb_1–y Bi _y )_2–x S₅, with 0.10 x 0.22 and 0.19 y 0.41. Fe-free, Bi-rich izoklakeite from Bazoges has high Ag contents (up to 2.2 wt. %), leading to the simplified formula Cu₂Pb₂₂Ag₂(Bi, Sb)₂₂S₅₇; in Les Chalanches it contains less Ag content (1.2 wt.%), but has an excess of Cu that gives the formula: Cu_2.00 (Cu_0.49Ag_1.18)_=1.67Pb_22.70(Bi_12.63Sb_8.99)_=21.62S_57.27.In tintinaite from Pedra Luz, the variation of the Fe/Cu ratio can be explained by the substitution: Cu + (Bi, Sb) Fe + Pb; Fe-free kobellite from Les Chalanches has a Cu-excess, corresponding to the formula Cu_2.81Ag_0.54Pb_9.88(Bi_10.37Sb_5.21)_=15.38S_35.09. Eclarite from the type locality, structurally related to kobellite, shows a Cu excess too. In natural samples of the kobellite homologous series, Fe is positively correlated with Pb, and its contents never exceed that of Cu. Ag substitutes for Pb, together with (Bi, Sb). Taking into account the possibility of Cu excess, but excluding formal Cu²⁺ and Fe³⁺, general formulae can be written:     

High-pressure metamorphism in metabasites from the Betic Cordilleras (S.E. Spain) and its evolution during the Alpine orogeny

The Nevado-Filábride complex is the lowest tectonic unit of the Betic Zone sensu stricto (ss) of the Betic Cordilleras (S.E. Spain). The upper series of this complex consists of a metamorphosed sequence intruded by basic and ultrabasic igneous rocks. High-pressure metamorphism in the eclogite and blueschist facies is recorded in the metabasites, but this was partially obliterated by further successive metamorphic stages in the almandine-amphibolite and greenschist facies.Coronitic and granoblastic eclogites appear side by side in the large stocks of basic rocks. The coronitic eclogites originate from coarse-to medium-grained olivine gabbros, and the granoblastic eclogites from fine-grained basic rocks (dolerites and porphyritic basaltic rocks). Higher chemical mobility and rate of diffusion, as well as the availability of fluids during the eclogite facies metamorphism, are responsible for the greater degree of recrystallization found in the granoblastic eclogites. The availability of fluids during this metamorphic stage was controlled by the difference in the hydration of the protolith and by variable proximity to surrounding water-rich metasediments.The minerals in the eclogites are chemically homogeneous, suggesting that they are almost completely equilibrated, even in the coronitic eclogites. The estimated equilibrium P-T conditions were found to be the same (approximately 550° C at 12 kbar pressure) in both coronitic and granoblastic eclogites, and it has, therefore, been deduced that the coronitic eclogites do not represent the first and lower-grade step of a prograde metamorphism in which the granoblastic eclogites are the higher-grade step.No relationship was found between shearing and eclogite crystallization. Nevertheless, a first fabric/foliation developed in the later blueschist facies stage, and syntectonic growth of the minerals was detected in glaucophane-bearing rocks.The further metamorphic evolution of the metabasites from high-to intermediate-pressure conditions is documented by the formation of minerals belonging to albiteepidote and almandine-amphibolite facies assemblages. The application of the amphibole zonation model, in order to deduce the P-T path, does not give realistic values.High-pressure metamorphism is related to an early subduction event in the Betic Cordilleras, with a later more-or-less isothermal uplift to shallower levels.     

Minerals and calculated low-temperature phase equilibria in the pseudoternary system Tl2S-As2S3-Sb2S3

Summary The experimental determination of phase relations in the pseudoternary system Tl₂ S-As₂S₃-Sb₂S₃ below 200°C is practically impossible, especially so under dry condensed conditions. As thallium sulfosalts are naturally formed at low temperatures equilibrium phase assemblages at 100 and 200°C were calculated by application of thermochemical approximations for the free enthalpies of formation of the sulfosalts. A comparison of the calculated conode configurations with the results of syntheses under dry condensed conditions at 200°C yielded good agreement between experiment and calculations.

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Minerale und Phasenbeziehungen im pseudoternären System Tl₂S-As₂S₃-Sb₂S₃ bei tiefen Temperaturen

Zusammenfassung Die Ableitung der Phasenbeziehungen im pseudoternären System Tl₂S-As₂S₃-Sb₂S₃ für Temperaturen unterhalb 200°C, insbesondere unter trockenen Bedingungen, ist auf experimentellem Weg praktisch nicht möglich. Da die Thalliumsulfosalze als tieftemperierte Mineralbildungen anzusehen sind, wurden die stabilen Gleichgewichtsassoziationen bei 100 und 200°C unter Verwendung thermodynamischer Näherungen für die freie Bildungsenthalpie der Sulfosalze berechnet. Ein Vergleich der berechneten Konodenverläufe mit den Ergebnissen von Versuchen unter trocken kondensierten Bedingungen bei 200°C ergab gute Übereinstimmung zwischen Experiment und Berechnung.

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Surface complexation of Pb(II) by hexagonal birnessite nanoparticles

Natural hexagonal birnessite is a poorly crystalline layer type Mn(IV) oxide precipitated by bacteria and fungi which has a particularly high adsorption affinity for Pb(II). X-ray spectroscopic studies have shown that Pb(II) forms strong inner-sphere surface complexes mainly at two sites on hexagonal birnessite nanoparticles: triple corner-sharing (TCS) complexes on Mn(IV) vacancies in the interlayers and double edge-sharing (DES) complexes on lateral edge surfaces. Although the TCS surface complex has been well characterized by spectroscopy, some important questions remain about the structure and stability of the complexes occurring on the edge surfaces. First-principles simulation techniques such as density functional theory (DFT) offer a useful way to address these questions by providing complementary information that is difficult to obtain by spectroscopy. Following this computational approach, we used spin-polarized DFT to perform total-energy-minimization geometry optimizations of several possible Pb(II) surface complexes on model birnessite nanoparticles similar to those that have been studied experimentally. We first validated our DFT calculations by geometry optimizations of (1) the Pb-Mn oxyhydroxide mineral, quenselite (PbMnO₂OH), and (2) the TCS surface complex, finding good agreement with experimental structural data while uncovering new information about bonding and stability. Our geometry optimizations of several protonated variants of the DES surface complex led us to conclude that the observed edge-surface species is very likely to be this complex if the singly coordinated terminal O that binds to Pb(II) is protonated. Our geometry optimizations also revealed that an unhydrated double corner-sharing (DCS) species that has been proposed as an alternative to the DES complex is intrinsically unstable on nanoparticle edge surfaces, but could become stabilized if the local coordination environment is well-hydrated. A significant similarity exists in the structural parameters for the TCS complex and those for a DCS edge-surface complex that is protonated in the same manner as the optimal DES complex, which could complicate detecting the DCS complex in X-ray absorption spectra.