Luca Bindi

Five-dimensional structure refinement of natural melilite, (Ca1.89Sr0.01Na0.08K0.02)(Mg0.92Al0.08)(Si1.98Al0.02)O7

The structure of a crystal of natural melilite from San Venanzo, Umbria (Italy) of the general formula X2T1(T2)2O7, where X = Ca0.945Sr0.005Na0.04K0.01, T1 = Mg0.92Al0.08 and T2 = Si0.99Al0.01, has been solved and refined as an incommensurate structure in five-dimensional superspace. The structure is tetragonal, superspace group P\bar 421m:p4mg, cell parameters a = 7.860 (1), c = 5.024 (1) A, modulation vectors q1 = 0.2815 (3)(a* + b*), q2 = 0.2815 (3)(−a* + b*). The data collection was performed on a KumaCCD diffractometer. The structure was refined from 7606 reflections to final R = 0.0481. A special modification of the refinement program Jana2000 was necessary to take into account overlapping of satellite reflections m × n = ±1, which could not be properly separated in the integration procedure. The final model includes modulations of the atomic positions as well as modulations of the thermal parameters. The latter are induced by strong differences in the neighbourhood of the actual modulated positions. The occupational modulation was neither significant for X nor for T1 sites and the sites were supposed to be occupied only by Ca and Mg, respectively. As a consequence of the Ca and O positional modulations six-, seven- and eightfold Ca coordination occur throughout the structure and the thermal ellipsoid changes its shape correspondingly. The positional modulation of the atoms causes variations in the interatomic distances which, however, do not affect bond-valence sums considerably, but induce flattening and rotation in T1 and T2 tetrahedra, respectively.

Icosahedrite, Al63Cu24Fe13, the first natural quasicrystal

Abstract Icosahedrite, ideally Al63Cu24Fe13, is a new mineral from the Khatyrka River, southeastern Chukhotka, Russia. It occurs as dark gray-black anhedral to subhedral grains up to 100 μm across, closely associated with spinel, diopside, forsterite, nepheline, sodalite, corundum, stishovite, khatyrkite, cupalite, and an unnamed phase of composition AlCuFe. Icosahedrite is opaque with a metallic luster, possesses a gray streak, and is brittle with an uneven fracture. The density could not be determined. For quasicrystals, by definition, the structure is not reducible to a single three-dimensional unit cell, so neither cell parameters nor Z can be given. In plane-polarized incident light, icosahedrite exhibits neither bireflectance nor pleochroism. Between crossed polars, it is isotropic. Reflectance percentages (Rmin = Rmax) for the four standard COM wavelengths are 62.3 (471.1 nm), 60.6 (548.3 nm), 58.1 (586.6 nm), and 56.0 (652.3 nm), respectively. The X-ray powder pattern was indexed on the basis of six integer indices, as conventionally used with quasicrystals, where the lattice parameter (in six-dimensional notation) is measured to be a6D = 12.64 Å, with probable space group Fm3 5̄̄. The four strongest X-ray powder-diffraction lines [d in Å (I/I0) (n1,n2,n3,n4,n5,n6)] are: 2.006 (100) (420 042), 2.108 (90) (422̄ 2̄22), 1.238 (30) (604̄ 064), and 3.41 (25) (311̄ 1̄11). Average results of 34 electron-microprobe analyses gave, on the basis of total atoms = 100, the formula Al63.11Cu24.02Fe12.78Si0.03Co0.01Ca0.01Zn0.01Cr0.02Cl0.01. The simplified formula is Al63Cu24Fe13, which requires the mass fractions Al 43.02, Cu 38.60, Fe 18.38, total 100.00 wt%. The new mineral is named for the icosahedral symmetry of its internal atomic structure, as observed in its diffraction pattern. Both the new mineral and mineral name have been approved by the Commission on New Minerals, Nomenclature and Classification, IMA (2010-042).

Crystal chemistry of clinopyroxene from alkaline undersaturated rocks of the Monte Vulture Volcano, Italy

Abstract The Monte Vulture is a Late Pleistocene stratovolcano, composed of highly undersaturated alkaline potassic to ultrapotassic rocks belonging to the Roman Magmatic Province. These rocks are notably richer in Na2O if compared to similar rocks of the Roman Province. Two distinct magmatic Series have been recognized: (1) feldspar-bearing series, ranging from basanite to phonolite, and a volumetrically subordinate (2) feldspar-free series, consisting of melilitite, melafoidite, and hauynophyre. The clinopyroxene compositions of the feldspar-bearing series ranges from diopside to ferro-salite (hedenbergite), and shows, from basanite to phonotephrite, increasing FeOtot, Al2O3, and TiO2 and decreasing of MgO contents. Clinopyroxene in basanites and tephrites has generally high Fe3+ contents, which is typical for clinopyroxene from the Roman Province. Clinopyroxene of the feldspar-free series shows a more restricted variation in MgO, and has often very high Al2O3, FeOtot, and TiO2 contents. In all the crystals examined the Al3+ content is high and is present mostly on the T site and for a minor part on the M1 site. The M1–O2 distance shows a good correlation with the RM13+ content; clinopyroxene from basanites (feldspar-bearing series) has the lowest RM13+ and that from melilitite and hauynophyre (feldspar-free series) the highest RM13+ contents. Clinopyroxene crystals from feldspar-free rocks have smaller M1 and larger T polyhedral volumes when compared to those in olivine–melilitites and melilitites (kamafugites) from Umbria, but they show similar polyhedral volumes as clinopyroxene crystals from leucite-bearing rocks. Although clinopyroxene from feldspar-free rocks has small M1 volumes due to the high R3+ contents, M1 volumes of clinopyroxene from melilitites are larger than expected because of the higher (Fe3+/Al3+)M1 values. This larger M1 volume of clinopyroxene in melilitites causes a shortening of and a lengthening of the M2–O3 distance. Strong compositional and structural similarities between clinopyroxene of Monte Vulture and Leucite-bearing rocks of the Roman Province (plagioclase-bearing High Potassium Series=HKS) indicate a common petrogenetic affinity. On the other hand, differences between clinopyroxene in feldspar-free rocks from Monte Vulture and that in kamafugites (i.e, olivine melilitites, kalsilitites) from Central Italy, suggest significant magma dissimilarities between these two groups.

Evidence for the extraterrestrial origin of a natural quasicrystal.

We present evidence that a rock sample found in the Koryak Mountains in Russia and containing icosahedrite, an icosahedral quasicrystalline phase with composition Al63Cu24Fe13, is part of a meteorite, likely formed in the early solar system about 4.5 Gya. The quasicrystal grains are intergrown with diopside, forsterite, stishovite, and additional metallic phases [khatyrkite (CuAl2), cupalite (CuAl), and β-phase (AlCuFe)]. This assemblage, in turn, is enclosed in a white rind consisting of diopside, hedenbergite, spinel (MgAl2O4), nepheline, and forsterite. Particularly notable is a grain of stishovite (from the interior), a tetragonal polymorph of silica that only occurs at ultrahigh pressures (≥10 Gpa), that contains an inclusion of quasicrystal. An extraterrestrial origin is inferred from secondary ion mass spectrometry 18O/16O and 17O/16O measurements of the pyroxene and olivine intergrown with the metal that show them to have isotopic compositions unlike any terrestrial minerals and instead overlap those of anhydrous phases in carbonaceous chondrite meteorites. The spinel from the white rind has an isotopic composition suggesting that it was part of a calcium-aluminum-rich inclusion similar to those found in CV3 chondrites. The mechanism that produced this exotic assemblage is not yet understood. The assemblage (metallic copper-aluminum alloy) is extremely reduced, and the close association of aluminum (high temperature refractory lithophile) with copper (low temperature chalcophile) is unexpected. Nevertheless, our evidence indicates that quasicrystals can form naturally under astrophysical conditions and remain stable over cosmic timescales, giving unique insights on their existence in nature and stability.

A crystallographic review of arsenic sulfides : effects of chemical variations and changes induced by exposure to light

Crystal data for natural and synthetic arsenic sulfides are reported and discussed. Most of them [α- and β-dimorphite, realgar, β-As4S4 phase, pararealgar, Kutoglu’s As4S4(II) phase, alacranite, uzonite, orthorhombic As4S5 phase] have a crystal structure consisting of a packing of cage-like, covalently bonded As4Sn (n = 3, 4 and 5) molecules held together by weak interactions of van der Waals character. Their structures are compared in terms of molecular packing and molecular parameters. The layered structural arrangement of orpiment, As2S3, is described and the effects of the incorporation of Se replacing for S is discussed. The structures of wakabayashilite and getchel lite, which contain mixed (As, Sb) coordination polyhedra, are also described to outline the geometric effects of the Sb → As substitution. The results of recent studies dealing with the effects of the exposure of realgar or other arsenic sulfides to visible light are reported and discussed. Their interest in the study of arsenical pigments and their preservation in artwork is outlined with some examples of application.

Natural quasicrystal with decagonal symmetry

We report the first occurrence of a natural quasicrystal with decagonal symmetry. The quasicrystal, with composition Al71Ni24Fe5, was discovered in the Khatyrka meteorite, a recently described CV3 carbonaceous chondrite. Icosahedrite, Al63Cu24Fe13, the first natural quasicrystal to be identified, was found in the same meteorite. The new quasicrystal was found associated with steinhardtite (Al38Ni32Fe30), Fe-poor steinhardtite (Al50Ni40Fe10), Al-bearing trevorite (NiFe2O4) and Al-bearing taenite (FeNi). Laboratory studies of decagonal Al71Ni24Fe5 have shown that it is stable over a narrow range of temperatures, 1120 K to 1200 K at standard pressure, providing support for our earlier conclusion that the Khatyrka meteorite reached heterogeneous high temperatures [1100 < T(K) ≤ 1500] and then rapidly cooled after being heated during an impact-induced shock that occurred in outer space 4.5 Gya. The occurrences of metallic Al alloyed with Cu, Ni, and Fe raises new questions regarding conditions that can be achieved in the early solar nebula.

In search of natural quasicrystals

The concept of quasicrystals was first introduced twenty-eight years ago and, since then, over a hundred types have been discovered in the laboratory under precisely controlled physical conditions designed to avoid crystallization. Yet the original theory suggested that quasicrystals can potentially be as robust and stable as crystals, perhaps even forming naturally. These considerations motivated a decade-long search for a natural quasicrystal culminating in the discovery of icosahedrite (Al(63)Cu(24)Fe(13)), an icosahedral quasicrystal found in a rock sample composed mainly of khatyrkite (crystalline (Cu,Zn)Al(2)) labeled as coming from the Koryak Mountains of far eastern Russia. In this paper, we review the search and discovery, the analysis showing the sample to be of extraterrestrial origin and the initial results of an extraordinary geological expedition to the Koryak Mountains to seek further evidence.

Impact-induced shock and the formation of natural quasicrystals in the early solar system

The discovery of a natural quasicrystal, icosahedrite (Al63Cu24Fe13), accompanied by khatyrkite (CuAl2) and cupalite (CuAl) in the CV3 carbonaceous chondrite Khatyrka has posed a mystery as to what extraterrestrial processes led to the formation and preservation of these metal alloys. Here we present a range of evidence, including the discovery of high-pressure phases never observed before in a CV3 chondrite, indicating that an impact shock generated a heterogeneous distribution of pressures and temperatures in which some portions reached at least 5 GPa and 1,200 °C. The conditions were sufficient to melt Al-Cu-bearing minerals, which then rapidly solidified into icosahedrite and other Al-Cu metal phases. The meteorite also contains heretofore unobserved phases of iron-nickel and iron sulphide with substantial amounts of Al and Cu. The presence of these phases in Khatyrka provides further proof that the Al-Cu alloys are natural products of unusual processes that occurred in the early solar system.

Temperature dependence of the silver distribution in the crystal structure of natural pearceite, (Ag,Cu)16(As,Sb)2S11.

The crystal structure of the mineral pearceite, (Ag,Cu)16(As,Sb)2S11, has been solved and refined at 300, 120 and 15 K. At room temperature pearceite crystallizes with trigonal symmetry, space group P3m1; the refinement of the structure leads to a residual factor of R = 0.0464 for 1109 independent observed reflections and 92 variables. The crystal structure consists of sheets stacked along the c axis. The As atoms form isolated (As,Sb)S3 pyramids, which typically occur in sulfosalts, copper cations link two S atoms in a linear coordination, and the silver cations are found in a fully occupied position and in various sites corresponding to the most pronounced probability density function locations (modes) of diffusion-like paths. These positions correspond to low-coordination (2, 3 and 4) sites, in agreement with the preference of silver for such environments. d10 silver-ion distribution has been determined by means of a combination of a Gram-Charlier description of the atomic displacement factors and a split-atom model. To analyse the crystal chemical behaviour of the silver cations as a function of temperature, a structural study was carried out at 120 K (R = 0.0450). The refinement indicates that the mineral exhibits the same structural arrangement as the room-temperature structure (space group P3m1) and shows that the silver cations are still highly disordered. In order to investigate a possible ordering scheme for the silver cations, a data collection at ultra-low temperature (15 K) was performed. The structural skeleton was found to be similar to that of the room-temperature and 120 K atomic structures, but the best solution was achieved with a fully split-atom model of five silver positions, giving an R value of 0.0449 for 651 observed reflections and 78 parameters. Although the silver cation densities condense into better defined modes, the joint probability density function still exhibits a strong overlapping of neighbouring sites.

Ultrapotassic clinopyroxene from the Kumdy-Kol microdiamond mine, Kokchetav Complex, Kazakhstan: Occurrence, composition and crystal-chemical characterization

Abstract We report data on the composition and crystal structure of the most K-rich (3.61 wt% K2O) natural clinopyroxene yet discovered. The studied crystal was found as a tiny inclusion in garnet from a garnet-clinopyroxene rock of the Kumdy-Kol microdiamond mine, Kokchetav complex, Northern Kazakhstan. Microprobe analysis yields the formula (Ca0.61Fe0.13Mg0.04Mn0.01K0.17Na0.05) (Al0.61Mg0.39)(Si1.61Al0.39)O6.00. Lattice parameters are: a = 9.773(1), b = 8.926(1), c = 5.269(1) Å, β = 105.75(1)°. The structure was refined up to Rall = 2.42% using 982 independent reflections. Substitution of K for Ca causes significant modification of the average structure. No evidence for an additional M2’ position was found. Crystal-chemical characteristics are compared with published data on both natural and synthetic K-bearing clinopyroxenes.