Childrenite and crandallite from the Stari Trg mine (Trepča), Kosovo: new data

Summary Childrenite and crandallite are described as two new phosphate members in the paragenesis of the Stari Trg mine which comprises vivianite, ludlamite and struvite. Crandallite crystals with very simple rhombohedral habit grow on rhombohedral carbonate and childrenite crystals. The crystal morphology of childrenite is very similar to that at described from other localities. Following forms were measured: {100}, {100}, {110}, {120}, {121}, {221} and {342}. The average chemical composition is Ch₉₁ Eo₉ (Ch-childrenite, Eo-eosphorite). Pseudo-orthorhombic unit cell dimensions were calculated: a = 10.390(4) A, b = 13.390(4) A and c = 6.920(2) A. Growth sectors and sector twins of childrenite are described.

---

Childrenit und Crandallit aus der Stari Trg Grube (Trepa), Kosovo: Neue Daten

Zusammenfassung Childrenit und Crandallit werden als zwei neue Minerale der Phosphatgruppe beschrieben. Sie stammen aus der Stari Trg Grube in Paragenese mit Vivianit, Ludlamit und Struvit. Die Crandallit-Kristalle mit einfachem rhomboedrischen Habitus, wachsen rhomboedrischen Karbonat- und Childrenit-Kristallen auf. Die Kristallmorphologie von Childrenit ist, verglichen mit der aus anderen Lokalitäten, sehr einfach. Folgende Formen wurden gemessen: {100}, {010}, {110}, {120}, {121}, {221} und {342}. Die durchschnittliche chemische Zusammensetzung ist Ch(₉₁Eo₉(Ch-Childrenit, Eo Eosphorit). Eine Kalkulation der pseudo-orthorhombischen Elementarzelle ergab folgende Abmessungen: a = 10.390(4) A, b = 13.390(4) A and c = 6.920(2) A. Schließlich wird das Wachstum and die Zwillingsbildung von Childrenit beschrieben.

---

---

With 4 Figures     

Inclusions of metal solvent and color of boron-bearing monocrystals of synthetic diamond

Cuboctahedral diamond monocrystals of physical classification type IIb weighing from 0.1 to 2 carats and with minor faces {110}, {311}, and {511} have been synthesized. The crystals are characterized by various hues of blue and dark blue depending on the amount of B in the system. A characteristic feature of these diamonds is a sectorial structure expressed in a nonuniform color distribution. The following types of metallic inclusions in the crystals have been recognized: faceted isometric, lamellar, and extended inclusions; unfaceted irregular and drop-shaped inclusions; and microinclusions. These inclusions are related to the chemical composition of the metal solvent.     

Systematics of internal zircon morphology in major Variscan granitoid types

The internal morphologies of zircon crystals from different types of granitoids (alkaline, calcalkaline and anatectic) are revealed by cathodoluminescence imaging and are described in terms of growth rates of the crystal faces relative to each other. Zircons in the alkaline granitoids are characterized by high and constant growth rates of {010} relative to the pyramidal forms and by symmetric grwoth of {011}. Zircons in the calcalkaline and anatectic granitoids are characterized by fluctuating or gradually decreasing relative growth rates of {010}, by asymmetric and highly variable growth of {011}, and by a tendency of {110} to become grwoth-inhibited. Corrosion events are interspersed during zircon growth in the calcalkaline magmas. In the calcalkaline and anatectic magmas, a discontinuity breaks the morphological evolution at late stages of crystallization. The discontinuity coincides with a sharp drop in cathodoluminescence. The growth behaviour of each crystal form is analysed and compared with predictions made by the periodic bond chain (PBC) theory. It is argued that the relative growth rate of {010} depends on supersaturation, that the growth rates of {011} faces are changed in response to different ratios of adsorbing cations (Na, K, Al), and that {110} faces become growth-inhibited by the adsorption of H₂O or trace elements enriched in the residual liquid. Morphological and chemical discontinuities at late stages of crystallization are reasonably explained by the formation of larger growth units (from smaller ionic entities) in the residual liquid. Important factors controlling the zircon morphology in different types of granitoids are: high cooling rates (alkaline magmas), magma mixing (calcalkaline magmas), enrichment of H₂O and trace elements in residual liquids (calcalkaline and anatectic magmas), and the major element chemistry of the magma, possibly the ratio of Na and K to Al (agpaicity).     

锡石的晶体结构和形态的关系

本文对不同成因类型的锡石晶体形态进行了研究,并从PBC(周期性键链)理论出发,讨论了锡石晶体形态与晶体结构的关系。笔者认为,锡石晶体具有三种F面,即s{111}、e{101}、m{110},与Hartman对同样结构类型的金红石晶面性质划分有所差异。据锡石晶面结构性质所推导的理想晶体形态图,与晶体测量所得到的天然晶体形态图总体上相吻合。     

Chromatographic study of formation conditions of rhombododecahedral diamond crystals

The results of chromatographic study of the formation of rhombododecahedral diamonds synthesized in the Fe-Ni-(Ti)-C system at 5.5–6.0 GPa and 1350–1450°C are presented, including crystals with rounded surfaces of the rhombododecahedron with parallel striation, which are morphological analogues of natural diamonds abundant at various kimberlite, lamproite, and placer deposits. Chromatography was performed at 150°C with mechanical breakup of diamonds. The stable release of methane when diamonds of habit {110} are crushed is established. It is concluded that the appearance of the habit rhombododecahedron may be related not only to the effect of temperature and pressure on crystal growth but also to reductive conditions of crystallization. At the same time, the appearance of significant amounts of hydrocarbons in the system probably results in stopping of the growth of faces {110} and {100} and, instead, formation of specific surfaces that are composed of microscopic accessories faced by planes {111}.     

黄铁矿成因形态学

在1981—1986年野外工作的基础上,作者对胶东三县四个金矿床黄铁矿晶体形态进行了系统研究,对其中2495粒晶体进行了统计,对300粒晶体进行了测角,对60粒晶体进行了微形貌观察。根据以上实际工作及国内外有关资料提出了黄铁矿晶休常见单形出现频率的定量资料与晶体微形貌的特点,特别是{210}面上负条纹的特征与成因探讨。并讨论了黄铁矿晶体形态与分带性,与形成温度,与主、微量成分,与共生组合及与矿化等的关系。查明黄铁矿形态及其晶面微形貌的发育与硫逸度、温度、冷却速度等密切相关。在以上基础上提出了胶东四个金矿床中蚀变岩型金矿及石英脉型金矿两种成因类型黄铁矿形态特征上的五点差异。最后对黄铁矿研究方法要点进行了总结。     

Nucleation and crystallization of otavite, witherite, calcite, strontianite, hydrozincite, and hydrocerussite by CO2 membrane diffusion technique

Otavite, witherite, calcite, strontianite, hydrozincite and hydrocerussite nucleation was induced by CO₂ diffusion through a polyethylene membrane into a metal bearing solution. Nucleation and ongoing precipitation was followed at 25 ± 1 °C by the chemical evolution of the solution and the consumption of sodium hydroxide (pH-stat conditions). X-ray diffraction patterns as well as FT-infrared and Raman spectra confirmed the formation of well crystallized solids, except for less crystalline hydrozincite. In several experiments simonkolleite and laurionite precipitated concurrently with hydrozincite and hydrocerussite. The carbonate end-member minerals, smithsonite and cerussite, however were not formed. Carbonate minerals crystallized as spherical aggregates of thin layered otavite, spherical orientated witherite needles, rhombohedral calcite, pseudo-hexagonal strontianite laths, fibrous lumps of hydrozincite and planar hexagonal hydrocerussite crystals. Crystal and aggregate sizes range between 1 and 100 μm. Nucleation occurred at well defined reaction times and distinct critical supersaturation indices (SI_crit). The time for nucleation at constant pH decreased as the initial metal concentration increased for a given solid. The SI_crit values decreased in the order of hydrocerussite (3.2), otavite (2.5), strontianite (1.6), witherite (0.9) and calcite (0.7).     

Molecular-scale surface processes during the growth of calcite in the presence of manganese

This paper deals with the growth behaviour of the Mn-Ca-CO₃-H₂O solid solution-aqueous solution system on calcite {104} surfaces. This system represents a model example, which allows us to study the effect of a number of controlling factors on the crystallisation: (1) the supersaturation function, β(x), and nucleation rate function, J(x), for the Mn-Ca-CO₃-H₂O system, (2) the relationship of such functions to the molecular scale growth mechanisms operating on growing surfaces, and (3) the surface structure of the calcite {104} faces. In situ atomic force microscopy (AFM) growth experiments revealed a wide variety of surface phenomena, such as the transition between growth mechanisms, anisotropic changes in the step rates, and the influence of the Mn-bearing newly formed surface on subsequent growth (step stoppage followed by the formation of two-dimensional nuclei and the reproduction of the original calcite {104} surface microtopography). These phenomena result from the interplay between the controlling parameters and are explained in those terms.     

江西漂塘钨矿床中黄玉的晶体形态特征

晶体形态是描述矿物最直观的数据。本文对江西漂塘钨矿床中的５个黄玉晶体进行了晶体测量、投影、计算和实际晶体的立体图绘制，并对其形态特征进行了分析和总结。     

Factors controlling the development of prism faces in granite zircons: a microprobe study

Based on microprobe work, we present arguments that the size relations of the two common prisms {100} and {110} of accessory granite zircons are strongly influenced by chemical factors. Magmatic growth zoning patterns, which we have studied by means of backscattered electron imaging in special zircon sections orientated perpendicular to the c-axis, do not support previous models which assumed temperature or the degree of ZrSiO₄ supersaturation to be the primary prism-form-directing factors. The element U, which usually occupies the Zr-sites of granite zircoms to some degree, is strongly suspected of producing an (adsorptive) growth-blocking effect for {110}-type faces thus creating crystals with {110}-dominated prism morphology. A second independent mechanism that is likely to form zircons with large {110} prisms is the common substitution Zr⁴⁺+Si⁴⁺ versus Y(REE) and P contents (relative to Zr) are, according to our model, predestinated to produce zircons with large {100} prisms and vice versa.Dedicated to Prof. Günther Frasl on the occasion of his seventieth birthday     

The influence of picocyanobacterial photosynthesis on calcite precipitation

This study assessed the role of picocyanobacterial photosynthesis in the induction of calcite precipitation. It aimed at establishing whether photosynthetic uptake of bicarbonate by Synechoccoccus cells leads to calcite nucleation. The precipitation of calcite was initiated by addition of previously washed cyanobacterial cells of Synechococcus strain PCC 7942 to solutions of calcium carbonate at different saturation levels with respect to calcite. Precipitation experiments were performed under controlled laboratory conditions in two set-ups: one in which photosynthesis was inhibited using a herbicide called Diuron and the other one in which photosynthesis was taking place. During the experiments, a pH meter monitored the pH and ion selective electrodes monitored concentrations of carbonate and calcium ions. The morphology of the precipitated crystals was analysed using Scanning Electron Microscopy. When the kinetics of calcium carbonate nucleation by the Synechococcus cells were compared for the two sets of experiments, there were very little differences. In fact, the induction times for precipitation reactions with photosynthesis were shorter due to the uptake of carbon dioxide. It is therefore, concluded that photosynthesis does not directly influence the nucleation of calcite at the surface of Synechococcus cells with sufficient supply of carbon dioxide, i.e. cells took up carbon dioxide and not bicarbonate. The microscopic observations, however, provided some evidence that picocyanobacterial cell walls act as a template for calcite nucleation.     

The morphology of calcite crystals grown in a porous medium doped with divalent cations

Calcite crystals were grown in the presence of small concentrations (50, 200, and 600 ppm) of divalent cations (Ba²⁺, Sr²⁺, Co²⁺ and Mn²⁺) in a silica hydrogel medium. The calcite crystals grown in the presence of cations larger than Ca²⁺ (Ba²⁺ or Sr²⁺) developed rhombohedral habits defined by {101¯4} form, similar to the morphology of calcite grown in a pure gel. SEM images show that growth on {101¯4} occurs by lateral advancement of layers bounded by macroscopic dendritic or jagged steps. In the case of calcite crystals grown in a gel doped with cations smaller than Ca²⁺ (Co²⁺ or Mn²⁺), a variety of morphologies was obtained, ranging from blocky crystals (at lower concentrations: 50 and 200 ppm) to peanut-like aggregates, spheres and spherulites (at 600 ppm). The macroscopic morphological characteristics of such doped calcite crystals reflect closely the growth behaviour of calcite {101¯4} surface at a nanoscale, reported by previous AFM studies. Morphological features have been interpreted on the basis of the modification of growing steps characteristics as a consequence of asymmetrical cation incorporation. The use of such morphologies as a criterion of biological activity is, therefore, unreliable.     

我国某细脉浸染型钼矿床内的淡红沸石及其成因

淡红沸石(Stellerite)是辉沸石族矿物之一种,曾在白令海峡中的苏联铜岛、美国阿拉斯加的朱诺、芬兰和苏联东外贝加尔的一些多金属矿床发现过。前人对淡红沸石着重进行了结晶学和热分析的研究,而对其地质产状和成因以及与有关矿化的关系相对少一些。到目前为止,我国还沒有对淡红沸石进行过报导。     

Theoretical growth morphology of whewellite CaC2O4·H2O

The morphological theory of Hartman and Perdok (1955, 1956) allows to deduce the character of a growth form {hkl} on the basis of structural data alone. Its application to the structure of whewellite leads to the identification of forms {100}, {010}, {021}, {011}, {12 \(\bar 1\) } and {121} which show during the growth a flat surface profile (flat forms F). These forms occur very frequently in the crystals we grew from pure aqueous solutions at supersaturation β≦1,90. Other forms, {001} and {10 \(\bar 1\) }, possibly show a double character (F or S, where S stays for related faces showing a stepped profile during the growth) according to the bonds assumed within some periodic bond chains (PBCs). Alternative ways of bonding water molecules lead to different structures of the same PBC. The different energy corresponding to these structures may explain the complex morphology of both natural and synthetic crystals grown at high β values.     

锆石形态标型特征及标型生长机制探讨

本文在系统总结归纳不同研究者对锆石形态标型特征的研究成果基础上，重点从晶体生长、晶体化学和地球化学理论为重点探讨了锆石形态标型特征的生长机制。研究表明：锆石晶体结构中不同的面网方向，其平面内的原子组成、比例、化学键联结和键力以及面网间距和密度都是有差别的，由此决定了锆石晶体在不同的结晶介质条件下，不同面网的生长速度发生改变，生成相应的晶形。例如，尽管碱性元素并不进入锆石晶格，但它们可以影响Ｚｒ、Ｓｉ、Ｏ离子的扩散速度，但是富钾和富钠的介质对锆石晶形发育的影响是有差别的，表现为：在富钾的介质中，将导致柱面的法向生长速度较锥面快得多，而锥面中，｛１１１｝的法向生长又较｛３１１｝快，由此决定了形成以｛３１１｝锥为主的双锥状晶体；在富钠的介质中，柱面和锥面都有一定程度的发育，但前者弱于后者，而柱面中，｛１００｝的法向生长较｛１１０｝慢，由此决定了形成以｛１００｝柱和｛１１１｝锥为主的短柱锥状晶体。根据类似方法，论证了其它形态标型特征的客观性，从而揭示了标型之间的内在联系和本质，展示了花岗岩研究中锆石形态标型特征应用推广的前景，也可为单颗粒锆石定年研究提供更多的分析应用价值     

Twinning induced by the rhombohedral to orthorhombic phase transition in lanthanum gallate (LaGaO3)

Phase-transformation-induced twins in pressureless-sintered lanthanum gallate (LaGaO₃) ceramics have been analysed using the transmission electron microscopy (TEM). Twins are induced by solid state phase transformation upon cooling from the rhombohedral to orthorhombic (o, Pnma) symmetry at ∼145°C. Three types of transformation twins {101} _o , {121} _o , and {123} _o were found in grains containing multiple domains that represent orientation variants. Three orthorhombic orientation variants were distinguished from the transformation domains converged into a triple junction. These twins are the reflection type as confirmed by tilting experiment in the microscope. Although not related by group–subgroup relation, the transformation twins generated by phase transition from rhombohedral to orthorhombic are consistent with those derived from taking cubic aristotype of the lowest common supergroup symmetry as an intermediate metastable structure. The r→ o phase transition of first order in nature may have occurred by a diffusionless, martensitic-type or discontinuous nucleation and growth mechanism.     

Crystal morphology and surface structures of orthorhombic MgSiO3 perovskite

Orthorhombic MgSiO₃ perovskite is thought to be the most abundant mineral in the mantle of the Earth. Its bulk properties have been widely studied, but many geophysical and rheological processes are also likely to depend upon its surface and grain boundary properties. As a first step towards modelling these geophysical properties, we present here an investigation of the structures and energetics of the surfaces of MgSiO₃-perovskite, employing both shell-model atomistic effective-potential simulations, and density-functional-theory (DFT) calculations. Our shell-model calculations predict the {001} surfaces to be the energetically most stable surfaces: the calculated value of the surface energy being 2.2 J/m² for the MgO-terminated surface, which is favoured over the SiO₂-terminated surface (2.7 J/m²). Also for the polar surfaces {111}, {101} and {011} the MgO-terminated surfaces are energetically more stable than the Si-terminated surfaces. In addition we report the predicted morphology of the MgSiO₃ perovskite structure, which is dominated by the energetically most stable {001} and {110} surfaces, and which appears to agree well with the shape of grown single crystals.     

Thermoluminescence,fluorescence and electron paramagnetic resonance properties of synthetic hydrothermal scheelites

Hydrothermal scheelite was synthesized using Na₂WO₄ · 2 H₂O mixed with CaCl₂ · H₂O, CaSO₄ · 2 H₂O or CaF₂ at different temperatures (270–720° C) and 10⁸ Pa. The morphology of the crystals depends on the starting products. The observed faces include the {112}, {114}, {011}, and {013} forms. Pure or REE doped scheelites were studied by thermoluminescence (TL), fluorescence and electron paramagnetic resonance (EPR). The main TL peaks are located near 88, 149, 216, 277, and 315 K. Results obtained with EPR or optical fluorescence have been correlated with TL measurements and show that the trivalent lanthanide elements substitute for calcium ions without site distortion. The differences in TL observed between Eu and the other doping elements are related to the greater stability of Eu²⁺ caused by X-irradiation.     

Salinity reflux and dolomitization of southern Australian slope sediments: the importance of low carbonate saturation levels

Anomalously saline waters in Ocean Drilling Program Holes 1127, 1129, 1130, 1131 and 1132, which penetrate southern Australian slope sediments, and isotopic analyses of large benthic foraminifera from southern Australian continental shelf sediments, indicate that Pleistocene–Holocene meso‐haline salinity reflux is occurring along the southern Australian margin. Ongoing dolomite formation is observed in slope sediments associated with marine waters commonly exceeding 50‰ salinity. A well‐flushed zone at the top of all holes contains pore waters with normal marine trace element contents, alkalinities and pH values. Dolomite precipitation occurs directly below the well‐flushed zone in two phases. Phase 1 is a nucleation stage associated with waters of relatively low pH (ca 7) caused by oxidation of H₂S diffusing upward from below. This dolomite precipitates in sediments < 80 m below the sea floor and has δ¹³C values consistent with having formed from normal sea water (? 1‰ to + 1‰ Vienna Pee Dee Belemnite). The Sr content of Phase 1 dolomite indicates that precipitation can occur prior to substantial metastable carbonate dissolution (< 300 ppm in Holes 1129 and 1127). Dolomite nucleation is interpreted to occur because the system is undersaturated with respect to the less stable minerals aragonite and Mg‐calcite, which form more readily in normal ocean water. Phase 2 is a growth stage associated with the dissolution of metastable carbonate in the acidified sea water. Analysis of large dolomite rhombs demonstrates that at depths > 80 m below the sea floor, Phase 2 dolomite grows on dolomite cores precipitated during Phase 1. Phase 2 dolomite has δ¹³C values similar to those of the surrounding bulk carbonate and high Sr values relative to Phase 1 dolomite, consistent with having formed in waters affected by aragonite and calcite dissolution. The nucleation stage in this model (Phase 1) challenges the more commonly accepted paradigm that inhibition of dolomitization by sea water is overcome by effectively increasing the saturation state of dolomite in sea water.