Electron microscope study of the humite minerals: II. Mn-rich specimens

The results of an electron-microscope study of the alleghanyite (Mn-humite) minerals differ in some respects from those previously reported for the Mg-rich humites. They again reveal coherent intergrowths of the group members, but in some cases with very dense lamellar faulting, especially in alleghanyite specimens from the Benallt mine, Wales. Some of these faults were higher members of the series which occurred as very thin lamellae one or two unit cells thick. Superstructures (ordered intergrowths at the unit-cell level) were very rare; one, which was an ordered intergrowth of alternating bands of manganhumite and sonolite (Mn-clinohumite), was observed. Complex intergrowths at this level, but without translational periodicity, were more common. Such fragments were often twinned polysynthetically. Many specimens yielded relatively large crystal fragments of more than one member of the series (but without coherent boundaries). In some cases leucophoenicite was also present.     

Boron in magnesium minerals of the humite group

Based on microprobe analysis and IR-spectroscopy of a representative collection of magnesium minerals of the humite group (282 samples from 80 various geological-genetic occurrences all over the world), it was shown for the first time that these minerals typically concentrate trace boron (from 0.5 to 4.9 wt % B₂O₃ in 63 samples). The diagnostic bands of B-O stretching vibrations in IF-spectra of magnesium minerals of the humite group occur within the 1170–1190, 1262–1289, and 1306–1331 cm^?1 ranges and are regularly shifted to the low frequencies in a norbergite-chondrodite-humite-clinohumite series. Boron isomorphically replaces silicon in tetrahedra, probably, by Pertsev’s scheme: Si⁴⁺ + O^2? → B³⁺ + (F,OH)^?.     

Electron microscope study of peridotite xenoliths in kimberlites

Dislocation structures in naturally deformed olivine from garnet peridotite xenoliths from South African kimberlites have been studied by electron microscopy. The substructure consists mainly of straight subboundaries of dislocations with Burgers vectors [001]. Most of the dislocations have both edge and screw components, and the slip planes are mainly (100). The dislocation density between the subboundaries is low.The slip planes in olivine are discussed in relation to the olivine structure. The observed dislocation structures seem to indicate that the large difference in strain rate between natural and experimental deformation will produce a difference in the slip mechanisms.The nature of the deformation lamellae visible in optical microscope is discussed.     

Electron microscope study of phase transformations in cubanite

Direct observations of the phase transformations in cubanite both on heating and cooling have been made in a transmission electron microscope. Low temperature orthorhombic cubanite undergoes a cation disordering process at about 200° C resulting in a hexagonal wurtzite type structure. The reordering process takes place by the growth of independently nucleated regions of short range order. Long range order is difficult to attain in short term experiments due to the lack of order correlation between regions. At a slightly higher temperature a transformation from hexagonal close-packing to cubic close-packing takes place within the sulphur structure, by the propagation of partial dislocations along alternate close-packing planes. This transformation is irreversible. On cooling the disordered cubic structure, cation ordering takes place as an alternative to the transformation back to hexagonal close-packing, but in the absence of an ordering scheme at this composition based on the cubic subcell, the ordering process results in the exsolution of chalcopyrite. This transformation is interpreted in terms of metastable, kinetically controlled behaviour.     

OH-bearing planar defects in olivine produced by the breakdown of Ti-rich humite minerals from Dabie Shan (China)

The partial breakdown of Ti-chondrodite and Ti-clinohumite during exhumation from ultra-high pressure to amphibolite facies conditions in garnet-pyroxenites from Dabie Shan (China) produces coronas of olivine coexisting with ilmenite blebs. Fourier transform infrared (FTIR) spectra of this newly formed olivine exhibit absorption bands in the hydroxyl-stretching region. Two intense peaks were observed at 3,564 and 3,394 cm⁻¹, identical in energy to peaks in Ti-clinohumite. Transmission electron microscopy (TEM) of the same olivine domains revealed the presence of a complex (001) planar intergrowth. These interlayers have a 1.35 nm repeat distance, which is characteristic of clinohumite. Such interlayers are also enriched in Ti with respect to the adjacent olivine as shown by energy dispersive spectrometry. The combined evidence from FTIR spectroscopy and TEM indicates that OH is incorporated along Ti-clinohumite planar defects. This study provides evidence that the nominally anhydrous phase olivine may contain OH as a humite-type defect beyond the breakdown of the hydrous humite minerals and confirms earlier suggestions that Ti plays a key role in OH incorporation in mantle olivine. We suggest that olivine containing Ti-clinohumite defects is an important phase for water transport in subduction zones and for the storage of water in cold subcontinental mantle. However, these defects are unlikely to be stable in hotter parts of the oceanic mantle such as where basaltic magmas are generated.     

江西雅山黄玉锂云母花岗岩中铯矿物的电子探针研究

江西宜春雅山花岗岩是典型的高度分异型稀有金属花岗岩。通过对其最晚期花岗岩———黄玉锂云母花岗岩的钻孔样品和近地表样品的研究,发现岩体中主要有两种铯矿物:铯沸石和富铯锂云母。铯沸石是第一次在花岗岩中发现,其产状主要有两类:一类包裹于石英中,颗粒小,只有2～10μm,单个颗粒成分均匀,Si/Al比值和Poll值(%)犤=100×Cs/(Na+K+Rb+Cs)犦分别为2.13～2.65和57～89;另一类赋存于钠长石晶隙间,颗粒大,多为几百μm,单个颗粒成分不均匀,Si/Al比值和Poll值分别为2.20～2.45和75.6～88.2。富铯的云母类矿物分布较普遍,主要呈四种产状,分别为钾长石雪球中的带状富铯锂云母、云母边部的环边富铯云母、叶脉纹理状富铯云母和主矿物中的富铯云母包裹体,并根据成分中Si/Al比值和Cs的摩尔分数(%)犤=100×Cs/(Cs+K)犦,将富铯的云母类矿物分为含铯锂云母、富铯锂云母和铯锂云母三类,其中Cs替代K,Cs完全替代K形成的铯锂云母可能是锂云母系列中的铯端员新矿物。钻孔样品中的富铯云母类矿物以带状结构和环边结构最为发育,且成分主要属于含铯锂云母和富铯锂云母这两个部分,而近地表样品中则以环边结构和叶脉纹理状结构为特征,成分多为铯锂云母。铯沸石和富铯云母的产状及地球化学特征均表明,雅山岩体原始岩浆中碱金属经     

Damage of topaz and other minerals in the electron microscope

Summary Hydroxyl bearing topaz suffers beam-damage in the electron microscope. Irradiation by the beam rapidly produces contrast from strain fields around small needle-shaped pores about 2–5 nm wide and 30–120 nm long, produced by the loss of hydrogen as water and/or hydrogen fluoride. In the majority of cases the damage ceases after a short period of time, and the topaz electron diffraction pattern remains apparently unchanged. In a few cases complete breakdown of the topaz occurs to produce mullite and/or fine-grained -alumina, the latter usually being sputtered onto the carbon support film. The different degrees of breakdown which are found in the electron beam are similar to reactions which occur on heating in air. Although the main factor which determines the degree of beam-induced damage which occurs is believed to be temperature, the heating effect of the beam is alone unlikely to cause the reactions. The lowering of reaction temperature is attributed to mechanically induced enhancement of diffusion in the electron beam and to the weakening of chemical bonds by ionisation effects. The strain fields found in topaz were also produced in samples of humite and apatite observed in the electron microscope, and the formation of fine-grained metal oxides was found in several silicates and phosphates.

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Zerstörung von Topas und anderen Mineralen im Elektronenmikroskop

Zusammenfassung Hydroxil-hältige Topase unterliegen im Elektronenmikroskop einer Zerstörung durch den Elektronenstrahl. Durch die Bestrahlung entstehen rasch Kontraste von gestörten Bereichen rund um kleine nadelförmige Poren von etwa 2–5 nm Durchmesser und 30–120 nm Länge, die durch den Verlust von Wasserstoff als Wasser und/oder Hydrogenfluorid verursacht werden. Meist hört die Zerstörung nach kurzer Zeit auf und das Elektronen-Beugungsbild des Topases bleibt anscheinend unverändert. In wenigen Fällen kommt es zu einem kompletten Zusammenbruch des Topases und es entsteht Mullit und/oder feinkörniges -Al₂O₃. Die unterschiedlichen Grade des Zusammenbruchs, die im Elektronenstrahl beobachtet werden, sind Reaktionen ähnlich, die beim Erhitzen in Luft auftreten. Obwohl als Hauptfaktor, der den Grad der Strahlinduzierten Zerstörung bestimmt, die Temperatur angenommen werden kann, ist es unwahrscheinlich, daß der Hitzeeffekt des Strahls allein die Reaktionen verursacht. Die Erniedrigung der Reaktionstemperatur wird der mechanisch bedingten Erhöhung der Durchdringungsfähigkeit des Elektronenstrahls und der Schwächung der chemischen Bindung durch Ionisierungseffekte zugeschrieben. Die im Elektronenmikroskop in Topas gefundenen gestörten Bereiche wurden auch in Proben von Humit und Apatit beobachtet; in verschiedenen Silikaten und Phosphaten wurde die Bildung feinkörniger Metalloxide gefunden.

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With 3 Figures

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Dedicated to Professor Dr.Josef Zemann on the occasion of his 6oth birthday.     

Domain wall formation in minerals: I. theory of twin boundary shapes in Na-feldspar

Domains of triclinic Na-feldspar which are a direct consequence of structural strain are investigated theoretically. The following conclusions are arrived at. Only two types of twin walls are created by spontaneous strain, namely the Albite- and Pericline twin walls. If intersections occur, rounded corners are predicted. Any third domain wall close to such an intersection must bend into an S-shape. Narrow domains between two twin walls tend to become needle-shaped close to the intersection with a further, perpendicular, twin wall. The combination of the elastic stiffness coefficients c ₄₄ c ₆₆-c ₄₆ ² is expected to become small at temperatures near to the transition temperature. In the same temperature interval elastic fluctuations occur; their amplitudes and propagation directions are given.     

Electron microscope investigation of the structure of naturally and artificially metamorphosed kerogen

The alteration of organic materials during burial is similar to thermally induced carbonization. High resolution electron microscopy shows that samples of either natural or heat-treated kerogens are formed by stacks of two aromatic layers of 5–8 Å in diameter. During catagenesis and heat-treatment, these stacks orientate themselves parallel to each other and form clusters of increasing diameter.     

基于深度学习的镜下矿石矿物的智能识别实验研究

矿石矿物鉴定的智能化是智能地质学和智能矿床学的基础技术之一。计算机视觉技术和深度学习理论使矿石矿物鉴定的智能化成为可能。本研究基于深度学习系统Tensor Flow,以吉林夹皮沟金矿和河北石湖金矿的黄铁矿、黄铜矿、方铅矿、闪锌矿等硫化物矿物为例,设计有针对性的Unet卷积神经网络模型,有效自动提取矿相显微镜下矿石矿物的深层特征信息,实现镜下矿石矿物智能识别与分类。实验显示,模型在训练过程中,随着训练次数的增加,模型精度在不断增大,损失函数不断减小;经过3000个批处理之后,模型精度和损失函数基本趋于稳定。训练出的模型对测试集中的显微镜镜下矿石矿物照片的识别成功率均高于90%,说明实验所建立的模型,具有很好的图像特征提取能力,能完成镜下矿石矿物智能识别的任务。     

Periodic Hartree-Fock study of minerals: Tetracoordinated silica polymorphs

Periodic Hartree-Fock STO-3G calculations have been performed on several tetracoordinated silica polymorphs: low and high quartz, low and idealized high cristobalite and prototype tridymite. The optimized structural parameters are in overall good agreement with experimental data. In the particular case of -quartz, the SiO₄ tetrahedra are found to be irregular. The optimized values of the two different SiO bond lengths are respectively 1.608 Å and 1.613 Å. The potential energy versus tilt angle curves suggest a picture of the high temperature phases in terms of delocalized oxygen atoms which is consistent with a disordered structure. Finally, the bonding in silica polymorphs is discussed from electron density maps and Mulliken population analysis.     

Recent progress in the study of accessory minerals

Mineralogy and Petrology -     

XPS spectra of uranyl minerals and synthetic uranyl compounds. I: The U 4f spectrum

The occurrence and binding energies of the U⁶⁺, U⁵⁺ and U⁴⁺ bands in the U 4f_7/2 peak of 19 uranyl minerals of different composition and structure were measured by XPS. The results suggest that these minerals can be divided into the following four groups: (1) Uranyl-hydroxy-hydrate compounds with no or monovalent interstitial cations; (2) Uranyl-hydroxy-hydrate minerals with divalent interstitial cations; (3) Uranyl-oxysalt minerals with (TO_n) groups (T = Si, P, and C) in which all equatorial O-atoms of the uranyl-polyhedra are shared with (TO_n) groups; (4) Uranyl-oxysalt minerals with (TO_n) groups (T = S and Se), in which some equatorial O-atoms are shared only between uranyl polyhedra. The average binding energies of the U⁶⁺and U⁴⁺ bands shift to lower values with (1) incorporation of divalent cations and (2) increase in the Lewis basicity of the anion group bonded to U. The first observation is a consequence of an increase in the bond-valence transfer from the interstitial species (cations, H₂O) groups to the O-atoms of the uranyl-groups, which results in an electron transfer from O to U⁶⁺. The second trend correlates with an increase in the covalency of the UO bonds with increase in Lewis basicity of the anion group, which results in a shift of the electron density from O to U. The presence of U⁴⁺ on the surface of uranyl minerals can be detected by the shape of the U 4f_7/2 peak, and the occurrence of the U 5f peak and satellite peaks belonging to the U 4f_5/2 peak. The presence of U⁴⁺ in some of the uranyl minerals and synthetics examined may be related to the conditions during their formation. A charge-balance mechanism is proposed for the incorporation of lower-valence U in the structure of uranyl minerals. Exposure of a Na-substituted metaschoepite crystal in air and to Ultra-High Vacuum results in dehydration of its surface structure associated with a shift of the U⁶⁺ bands to higher binding energies. The latter observation indicates a shift in electron density from U to O, which must be related to structural changes inside the upper surface layers of Na-substituted metaschoepite.     

Composition and chemical microprobe dating of U-Th-bearing minerals. Part I. Monazites from the Urals and Siberia

To develop chemical microprobe timing of U-Th-bearing minerals, monazite grains from several localities in the Ural and Siberia have been dated using upgraded measurement techniques and age calculation based on original software. The samples were taken from pegmatites of the Ilmeny Mountains and the Ilmeny-Vishnevy Mountains Complex in the South Urals; pegmatites from the Adui granitic pluton and its framework in the Central Urals; gneisses and granulites of the Taratash Complex in the South Urals; and felsic gneisses from the Transangara region of the Yenisei Ridge. Scrutiny of the composition, heterogeneity, and chemical substitution of U and Th ions is a necessary stage of chemical dating aimed at estimating the degree of closeness of the U-Th-Pb system and unbiased screening of analytical data. The results obtained have been compared with the known isotopic ages of the studied minerals; the compared data are satisfactorily consistent.     

High-pressure behaviour of serpentine minerals: a Raman spectroscopic study

Four main serpentine varieties can be distinguished on the basis of their microstructures, i.e. lizardite, antigorite, chrysotile and polygonal serpentine. Among these, antigorite is the variety stable under high pressure. In order to understand the structural response of these varieties to pressure, we studied well-characterized serpentine samples by in situ Raman spectroscopy up to 10 GPa, in a diamond-anvil cell. All serpentine varieties can be metastably compressed up to 10 GPa at room temperature without the occurrence of phase transition or amorphization. All spectroscopic pressure-induced changes are fully reversible upon decompression. The vibrational frequencies of antigorite have a slightly larger pressure dependence than those of the other varieties. The O–H-stretching modes of the four varieties have a positive pressure dependence, which indicates that there is no enhancement of hydrogen bonding in serpentine minerals at high pressure. Serpentine minerals display two types of hydroxyl groups in the structure: inner OH groups lie at the centre of each six-fold ring while outer OH groups are considered to link the octahedral sheet of a given 1:1 layer to the tetrahedral sheet of the adjacent 1:1 layer. On the basis of the contrasting behaviour of the Raman bands as a function of pressure, we propose a new assignment of the OH-stretching bands. The strongly pressure-dependent modes are assigned to the vibrations of the outer hydroxyl groups, the less pressure-sensitive peaks to the inner ones.     

Low-grade metamorphic alteration of feldspar minerals: a CL study

ABSTRACT Two styles of feldspar alteration – carbonatization and albitization – were investigated using a cathodoluminescence (CL) technique. The nature of the alteration depends on the composition of the fluids. The infiltration of CO₂-rich fluids causes decomposition of An-rich zones in plagioclase followed by the formation of secondary calcite, albite and white mica. K-feldspar is more resistant to CO₂-induced alteration. The circulation of aqueous fluids results in decomposition of primary oligoclase into albite and clinozoisite. Secondary K-feldspar exsolved as small independent grains on the rim of the primary oligoclase, if the primary plagioclase was enriched in the orthoclase component. The fluids easily penetrate the crystals using, crystallographic plains, e.g., twinning or cleavage or simply along cracks. These migration pathways enable the fluids to enter the inner parts of the grain, which would otherwise not be affected by grain-surface alteration.     

Mechanism of pyroxene and amphibole weathering—I. Experimental studies of iron-free minerals

The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca²⁺, Mg²⁺, and Si(OH)₄ and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M₂ structural sites. Loss mainly from M₂ sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca²⁺ and/or Mg²⁺ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on a_H⁺ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.     

Electron probe microanalysis of rock-forming minerals with a JXA-8100 electron probe microanalyzer

The protocol for analysis of rock-forming mineral compositions by X-ray electron probe microanalysis used at the Institute of Geology and Mineralogy, Novosibirsk, Russia, is described. The analysis is conducted with a JXA-8100 electron probe microanalyzer capable to support a highly stable beam at relatively high probe currents for a long time. Elements that can be assayed range from sodium (atomic number Z = 11) to zinc (Z = 30). The operation conditions for routine analyses are substantiated: accelerating voltage 20 kV, probe current 50–100 nA, and signal accumulation time 10 s at both the peak and the background. The method of analytical problem formulation for measurements is presented. It is proven that the proprietary software is insufficient with the presence of the binary matrix effect and better correction methods are required. Metrological characteristics of the protocol have been studied. The variation coefficient, describing the reproducibility of results, averages 0.9% for major components (C > 10%), 2.5% for minor components (1 < C < 10%), and 6.8% for accessory components (0.3 < C < 1%). With still lower contents (0.05 < C < 0.3 %), the standard deviation of reproducibility is 0.02%. The values of the variation coefficient and standard deviation for measurement repeatability are approximately two times lower. The relative trueness of the method is within 1%. The detection limit (3o criterion) is generally within 0.01-0.03%. It can be improved by an order of magnitude by increasing the accumulation time and probe current.     

Surface typochemistry of hydrothermal pyrite: Electron spectroscopic and scanning probe microscopic data. I. Synthetic pyrite

Techniques of X-ray photoelectron and Auger electron spectroscopy, scanning probe microscopy were used to demonstrate that the natural surface of hydrothermally synthesized pyrite, as well as vacuum fractures, contain a number of sulfide-sulfur species: disulfide, monosulfide, and, more rarely, polysulfide. The natural surface of hydrothermal pyrite is chemically modified compared to the inner volume into a nonautonomous phase film up to ～500 nm thick, which has a variable composition resembling that of pyrrhotite but with broader variations toward FeS₂. Its principal distinctive feature is the presence of a peak at ～710 eV in the XPS Fe 2p_3/2 spectrum, which is often higher than the main peak of bivalent low-spin Fe(II) in the pyrite structure (707 eV). The “basic” structure of the nonautonomous phase is a layer of variable composition Fe²⁺[S, S₂, S _n ]^2?, whose S/S₂ ratio varies from ～0.5 to ～2.0, averaging at ～1.1. This layer may include admixtures of minor elements, as follows from the appearance of a nonautonomous phase in the presence of As, which does not, however, form an individual phase. The polymerization of S at the surface is thereby more significant. The major oxisulfide components of this phase may be the sulfite and thiosulfate ions at a subordinate concentration of sulfate because of the instability of coexisting sulfate and disulfide ions, which results, in the presence of oxygen, in sulfite (thiosulfate) and sulfide ions in the nonautonomous phase. In line with XPS, scanning probe microscopic (SPM) data show that, at a high S activity in the “pure” system, the surface of the crystals contains practically no nanometer-sized phases and is characterized by low roughness (14–17 nm). At a low S fugacity in equilibrium with pyrrhotite and sphalerite, the average roughness of the surface increases to 25–65 nm, with the maximum height of the surface features of ～100–500 nm. This is consistent with Auger spectroscopic data, obtained after the etching (ion milling) of the surface with Ar⁺, on the thickness of the nonstoichiometric surface layer. Comparison with analogous data on other sulfides shows that crystals growing in hydrothermal environments have surface layers up to ～500 nm thick, which are different from the main volume of the crystal in chemistry, stoichiometry, and, possibly, also structure. This is scale of the surface heterogeneity at which the typochemistry of mineral surfaces may be manifested. The typochemistry of pyrite stems from the ability of the nonautonomous phase to “record” the growth conditions of crystals in terms of two major factors: the purity of the system (the occurrence of other phases, including virtual ones, i.e., potentially possible phases of admixture elements) and S fugacity (which influences the S/S₂ ratio at the surface). The geochemical role of the surface nonautonomous phase in pyrite may be very significant, particularly when minor elements are captured that are incompatible with the pyrite structure but can be easily accommodated in the less rigid structure of the nonautonomous phase.