Fresnoite: unusal titanium coordination

The crystal structure of fresnoite, Ba(2)(TiO)[Si(2)O(7)], consists of [Si(2)O(7)](6-) double groups and titanium-centered square pyramids linked to form flat sheets. Intercalated between these sheets are Ba(2+) ions in highly distorted pentagonal antiprisms. The structure of fresnoite is related to that of melilite, (Ca,Na)(2)(Mg,Al[Si(2)(7)].     

Tuhualite crystal structure

As judged by crystal structure analysis, the crystallochemical formula of tuhualite is (Na,K)(2)(VI) (Fe(+3))(2)(VI) (Fe(+2))(2)(VI) Si(12)O(30) . H(2)O, with four such formulas in the unit cell. The structure is characterized by six-repeat double chains of silicon tetrahedrons and chains of edge-sharing, alternating iron tetrahedrons and octahedrons. Chains of each kind are connected by corner sharing to four chains of the other type. The iron cations appear to be anomalously ordered with Fe(+2) in tetrahedral and Fe(+3) in octahedral sites.     

Eclogitic pyroxenes, ordered with p2 symmetry

X-ray diffraction crystal-structure analysis of omphacite from eclogite, Tiburon Peninsula, Marin County, California, shows that this clinopyroxene has P2 symmetry with a nearly ordered distribution of the multiple cation content defined by its approximate formula: (Na(o.5) Ca(o.5)) (Mg(o.4)Fe(2)+( 0.1) Al(0.4) Fe(3) +(0.1)) Si(2)0(6). Na+ and Ca(2+) tend to assume alternate locations in the structure, and ( Mg,Fe(2+)) octahedra alternate with Al(3+). or (Al,F(3+)) octahedra in chains along c.     

Periodic mesoporous organosilicas containing interconnected [Si(CH2)]3 rings

A periodic mesoporous organosilica composed of interconnected three-ring [Si(CH2)]3 units built of three SiO2(CH2)2 tetrahedral subunits is reported. It represents the archetype of a previously unknown class of nanocomposite materials in which two bridging organic groups are bound to each silicon atom. It can be obtained with powder and oriented film morphologies. The nanocomposite is self-assembled from the cyclic three-ring silsesquioxane [(EtO)2Si(CH2)]3 precursor and a surfactant mesophase to give a well-ordered mesoporous framework. Low dielectric constants and good mechanical stability of the films were measured, making this material interesting for microelectronic applications. Methylene group reactivity of the three-ring precursor provides entry to a family of nanocomposites, exemplified by the synthesis and self-assembly of [(EtO)2Si(CHR)][(EtO)2Si(CH2)]2 (where R indicates iodine, bromine, or an ethyl group).     

Anionic constitution of 1-atmosphere silicate melts: implications for the structure of igneous melts

A structural model is proposed for the polymeric units in silicate melts quenched at 1 atmosphere. The anionic units that have been identified by the use of Raman spectroscopy are SiO(4)(4-) monomers, Si(2)O(7)(6-) dimers, SiO(3)(2-) chains or rings, Si(2)O(5)(2-) sheets, and SiO(2) three-dimensional units. The coexisting anionic species are related to specific ranges of the ratio of nonbridging oxygens to tetrahedrally coordinated cations (NBO/Si). In melts with 2.0 < NBO/Si < approximately 4.0, the equilibrium is of the type [See equation in the PDF file]. In melts with NBO/Si approximately 1.0 to 2.0, the equilibrium anionic species are given by [See equation in the PDF file]. In alkali-silicate melts with NBO/Si <~ 1.3 and in aluminosilicate melts with NBO/T < 1.0, where T is (Si + Al), the anionic species in equilibrium are given by [See equation in the PDF file]. In multicomponent melts with compositions corresponding to those of the major igneous rocks, the anionic species are TO(2), T(2)O(5), T(2)O(6), and TO(4), and the coexisting polymeric units are determined by the second and third of these disproportionation reactions.     

An Inorganic Double Helix: Hydrothermal Synthesis, Structure, and Magnetism of Chiral [(CH3)2NH2]K4[V10O10(H2O)2(OH)4(PO4)7]{middle dot}4H2O

Very complicated inorganic solids can be self-assembled from structurally simple precursors as illustrated by the hydrothermal synthesis of the vanadium phosphate, [(CH(3))(2)NH(2)]K(4)[V(10)O(10)(H(2)O)(2)(OH)(4)(PO(4))(7)].4H(2)O, 1, which contains chiral double helices formed from interpenetrating spirals of vanadium oxo pentamers bonded together by P(5+). These double helices are in turn intertwined with each other in a manner that generates unusual tunnels and cavities that are filled with (CH(3))(2)NH(2)(+) and K(+) cations, respectively. The unit cell contents of dark blue phosphate 1, which crystallizes in the enantiomorphic space group P4(3) with lattice constants a = 12.130 and c = 30.555 angstroms, are chiral; only one enantiomorph is present in a given crystal. Magnetization measurements show that 1 is paramagnetic with ten unpaired electrons per formula unit at higher temperatures and that antiferromagnetic interactions develop at lower temperatures.     

Kaolinite: synthesis at room temperature

To obtain kaolinite at low temperature and pressure from the system Si(OH)(4)-Al(3+)-H(2)O, the sixfold coordination of aluminum is a necessary prerequisite. Kaolinite was synthesized at pH values from 2 to 9 and with a ratio of SiO(2) to Al(2)O(3) in solution from 1 to 10 by means of the complexation of Al(3+) and fulvic acid.     

Shattuckite and plancheite: a crystal chemical study

The orthorhombic crystal structures of shattuckite, Cu(5)( SiO(3))(4)(OH)(2) and planchétite, Cu(8)(Si(4)0(11))(2)(OH)(4) H(2)O, have been solved. Shattuckite contains silicate chains similar to pyroxene in a complex association with copper atoms, while the closely related planchéite contains silicate chains similar to amphibole.     

Staurolite: sectoral compositional variations

Electron-microprobe analyses across six successive sections of a single staurolite crystal show that the staurolite has three crystallographically controlled sectors, each with a distinctive content of Al, Si, Ti, Fe, Mg, and Mn. The sector distribution of elements raises the question of whether the staurolite acts as one or several phases during growth. Total analyses of the separate sectors suggest that: (i) the staurolite has tetrahedral Al substitution for Si, and (ii) the hydroxyl content varies beween sectors.     

Rhodizite: structure and composition

The mineral rhodizite could not be assigned a chemical formula on the basis of chemical analyses. The solution of the crystal structure reported here reveals that CsB(12)Be(4)Al(4)O(28) is the ideal formula. The oxygen atoms occupy all but four sites per cell of cubic close packing whose period is (1/2)a. The boron, beryllium, and aluminum atoms occupy interstices of this array, the first two in tetrahedral coordination, the last in octahedral coordination. Together these atoms form a continuous network whose composition is B(12)Be(4)Al(4)O(28), which should be neutral. The alkali atom is enclosed in a cage in this network and presumably is not behaving as an ion.     

First occurrence of the garnet-ilmenite transition in silicates

Pyrope garnet (Mg(3)Al(2)Si(3)O(12)) has been found to transform to an ilmenite-type phase at a loading pressure between 240 and 250 kilobars and at about 1000 degrees to 1400 degrees C in a diamond-anvil press coupled with laser heating. The lattice parameters for the ilmenite-type phase of (Mg(.75) Al(.25))(Si(.75) Al(.25))O(3) are a(0) = 4.755 +/- 0.002 and c(0) = 13.360 +/- 0.005 angstroms. The zero-pressure volume change associated with the garnet-ilmenite transition is calculated to be -7.1 percent. This result verifies the prediction that pyrope garnet would transform to the ilmenite structure at high pressure first suggested in 1962 by Clark et al. and Ringwood.     

The Effect of H2O on the 410-Kilometer Seismic Discontinuity

The 410-kilometer seismic discontinuity is generally considered to be caused by a phase transformation of the main constituent of the upper mantle, olivine, alpha-(Mg,Fe)(2)SiO(4), to beta-(Mg,Fe)(2)SiO(4). Recent data show that H(2)O dissolves in olivine and other nominally anhydrous mantle minerals and that the partitioning of H(2)O between olivine and beta-(Mg,Fe)(2)SiO(4) is about 1:10. Such behavior strongly affects the region over which the alpha to beta phase transformation occurs and hence the seismic discontinuity that results. The observed width of the discontinuity constrains the maximum H(2)O content of upper mantle olivine to about 200 parts per million by weight.     

Crystallographic orientation of clinoenstatite produced by deformation of orthoenstatite

Uniaxial compression at 800 degrees C and 5 kilobars confining pressure of a specimen cored from a single crystal of orthoenstatite [(Mg,Fe)SiO(3)] produced fine lamellae 100 to 1000 angstroms thick of untwinned clinoenstatite. The two phases are joined along (100) planes and have b and c axes in common. The orientation of the clinoenstatite a axis contradicts several previously suggested transformation mechanisms and reduces the set of possible mechanisms by a factor of 2.     

Ammonioborite: new borate polyion and its structure

The mineral ammonioborite is monoclinic with unit cell dimensions (in angstroms): a = 25.27, b = 9.65, and c = 11.56; beta = 94 degrees 17', and the space group is C 2/c. Analysis of the crystal structure revealed the crystallo-chemical formula (NH(4))(3)B(15)O(20)(OH)(8).4H(2)O, with four such formula units in the unit cell. The basic structural unit is the double ring consisting of one BO(4) tetrahedron and four BO(3) triangles: in ammonioborite three of these units are connected to give trimeric ions [B(15)O(20)(OH)(8)](3-).     

Direct observation of dissociated dislocations in garnet

Dislocation core structures in garnet [grossularite (Ca(2.9)Fe(II)(0.1))(Al(1.9)Fe(III)(0.1)Si(3.0)O(12)] have been examined with near atomic resolution transmission electron microscopy. Dissociated dislocations have been observed as parallel a/4<111> partial dislocations that are separated by stacking faults. The partial dislocations have narrow cores ( approximately 3 burgers vectors), and the stacking fault zone between the narrow partial dislocations is apparently a low-energy configuration that results from the occupancy of previously unfilled dodecahedral and tetrahedral sites. Previous studies of garnet dislocations suggested that dissociation involves departures from garnet stoichiometry (that is, trace amounts of impurities), but evidence of detectable amounts of impurities has not been found even in the highest resolution images. These results have implications for mantle mineral rheology and transformations as well as for ceramics of material science interest.     

Eight-membered cyclosilicate rings in muirite

The determination of the crystal structure of muirite, Ba(10)(Ca,Mn,Ti)(4)Si(8)O(24)(Cl,OH,O)(12) . 4H(2)O, revealed the presence of discrete cyclic silicate anions, (Si(8)O(24))(16-), formed by the condensation of eight silicate tetrahedra. This first reported occurrence of eight-membered rings is of particular interest, because rings with eight tetrahedra are reported to be energetically less stable than rings with six tetrahedra, which have been found in many minerals.     

Absence of neutral alkali atoms in rhodizite

The formula CsB(l2)Be(4)Al(4)O(28) has been proposed by others for the mineral rhodizite. Electron-spin-resonance and magnetic susceptibility measurements prove the absence of neutral cesium atoms. An ionic formula CsB(11)Be(4)Al(4)O(26)(OH)(2) is proposed.     

Kinetic evidence for five-coordination in AlOH(aq)2+ ion

Trivalent aluminum ions are important in natural bodies of water, but the structure of their coordination shell is a complex unsolved problem. In strong acid (pH < 3.0), Al(III) exists almost entirely as the octahedral Al(H2O)6(3+) ion, whereas in basic conditions (pH > 7), a tetrahedral Al(OH)(4- structure prevails. In the biochemically and geochemically critical pH range of 4.3 to 7.0, the ion structures are less clear. Other hydrolytic species, such as AlOH(aq)2+, exist and are traditionally assumed to be hexacoordinate. We show, however, that the kinetics of proton and water exchange on aqueous Al(III), coupled with Car-Parrinello simulations, support a five-coordinate Al(H2O)4OH2+ ion as the predominant form of AlOH(aq)2+ under ambient conditions. This result contrasts Al(III) with other trivalent metal aqua ions, for which there is no evidence for stable pentacoordinate hydrolysis products.     

The effect of alumina on the electrical conductivity of silicate perovskite

Measurements of the electrical conductivity of silicate perovskite at 25 gigapascals and 1400 degrees to 1600 degreesC show that the conductivity of (Mg,Fe)SiO3 perovskite containing 2.89 weight percent Al2O3 is about 3.5 times greater than that of aluminum-free (Mg0.915Fe0.085)SiO3 perovskite. The conduction mechanism in perovskite between 1400 degrees and 1600 degreesC is most likely by polarons, because Mossbauer studies show that the aluminum-bearing perovskite has about 3.5 times the amount of Fe3+ as the aluminum-free sample. A conductivity-depth profile from 660 to 2900 kilometers based on aluminum-bearing perovskite is consistent with geophysical models.     

海南岛火山岩砖红壤铁质风化壳主量元素特征[1]

通过对海南岛西北部火山岩砖红壤铁质风化壳剖面样品进行X荧光光谱法检测、风化特征指数及质量迁移系数的计算,揭示海南岛新生代火山岩砖红壤铁质风化壳的主量元素分布、风化强度和迁移特征。风化壳主量元素以Fe2O3、Al2O3、SiO2为主,K、Na、Ca、Mg等易溶组分较低;Fe2O3、Al2O3富集、SiO2淋失的热带地区风化特征。风化层CIA指数高达95%以上、Fe2O3/Al2O3上升,BA值较低, SiO2/Al2O3、SiO2/R2O3、BA下降;以Zr为参比元素,铁、铝迁移系数大于1,最大可达4.029,钠、钾、钙、镁、硅、锰迁移系数小于1,可低至-0.996。研究认为海南岛西北部火山岩风化壳表现为典型的脱硅富铁,铁质元素强烈富集,其它元素淋失明显,且铁铝元素发生了的分异,是比较成熟的风化壳。