Tonči Balić-Žunić

Eldfellite, NaFe(SO4)2, a new fumarolic mineral from Eldfell volcano, Iceland

Abstract A new mineral, eldfellite, was found among fumarolic encrustations collected in 1990 on the Eldfell volcano, Heimaey Island, Iceland. Associated minerals are ralstonite, anhydrite, gypsum, bassanite, hematite, opal and tamarugite, as well as a presumably new mineral with the composition Na3Fe(SO4)3. Along with opal and tamarugite, eldfellite forms soft and fragile aggregates built of thin, platy crystals of micrometre size. The mineral is yellowish-green to greenish-white, with a white streak. The calculated density is 3.062 g/cm3. Eldfellite is monoclinic, C2/m, a 8.043(4) Å, b 5.139(2) Å, c 7.115(4) Å, β 92.13(2)°, Vuc 293.9(2) Å3, Z = 2 and is isostructural with yavapaiite[KFe(SO4)2]. The strongest lines in the powder diffraction diagram are [d (Å), I (relative to 10)]: 3.72, 8; 3.64, 5; 3.43, 5; 2.77, 10; 2.72, 6; 2.57, 3; 2.370, 6; 1.650, 3. The chemical analysis and the X-ray diffraction data of eldfellite correspond to those of the synthetic compound NaFe(SO4)2.

Structure of the β form of calcium pyrophosphate tetrahydrate

β-Ca2P2O7·4H2O is monoclinic, P21/c, a = 12.287 (6), b = 7.511 (3), c = 10.775 (5) A, and β = 112.54 (1)°. Five of the terminal O atoms from a pyrophosphate group bind to Ca atoms, together with O atoms from three of the water molecules. The fourth H2O forms only hydrogen bonds. Both Ca atoms have coordination number 7 and show characteristics between those of a capped octahedron and a pentagonal bipyramid. The analysis of coordination distortions suggests that regularity and volume efficiency of a Ca coordination polyhedron increases with the number of bound water O atoms. The structure is layered after {100}, reflected also in the morphology of crystals which are formed as extremely thin plates. The central parts of the layers are formed by chains of Ca coordination polyhedra which run along the b axis and are interconnected by pyrophosphate groups. Water molecules form the surfaces of the layers. A peculiar auto-inhibition of growth from supersaturated solutions is supposed to be caused by a direct attachment of CaP2O72− and P2O74− to the water molecules on the surfaces of layers. Ca2P2O7·4H2O is known in two polymorphs. The unit-cell volume of the β form compared with that of α suggests that the former is a low-temperature modification.

Modular crystals as modulated structures: the case of the lillianite homologous series.

The use of the superspace formalism is extended to the description and refinement of the homologous series of modular structures with two symmetry-related modules with different orientations. The lillianite homologous series has been taken as a study case. Starting from a commensurate modulated composite description with two basic subsystems corresponding to the two different modules, it is shown how a more efficient description can be achieved using so-called zigzag modulation functions. These linear zigzag modulations, newly implemented in the program JANA2006, have very large fixed amplitudes and introduce in the starting model the two orientations of the underlying module sublattices. We show that a composite approach with this type of function, which treats the cations and anions as two separate subsystems forming a misfit compound, is the most appropriate and robust method for the refinements.

Re-investigation of the crystal structure of enstatite under high-pressure conditions

Abstract A synthetic single crystal of pure orthoenstatite (MgSiO3, space group Pbca) has been investigated at high pressure for structural determinations by in situ single-crystal X-ray diffraction using a diamond-anvil cell. Ten complete intensity data collections were performed up to 9.36 GPa. This study significantly improved the accuracy of structural parameters in comparison to a previous high-pressure structural study, allowing a more detailed examination of structural behavior of orthoenstatite at high pressures and a comparison to other more recent structural studies performed on orthopyroxenes with different compositions. The structural evolution determined in this work confirms the high-pressure evolution found previously for other orthopyroxenes and removes some ambiguities originating from the less accurate published data on the MgSiO3 structure at high pressure. The structural compression is mostly governed by significant volume decrease of the Mg1 and Mg2 octahedra, affecting in turn the kink of the tetrahedral chains, especially the TB chain of larger SiO4 tetrahedra. The Mg2 polyhedron undergoes the largest volume variation, 8.7%, due especially to the strong contraction of the longest bond distance (Mg2-O3B), whereas Mg1 polyhedral volume decreases by about 7.4%. The compressional behavior of the tetrahedral sites is quite different from previously published data. The TA and TB tetrahedral volumes decrease by about 2.8 and 1.8%, respectively, and no discontinuities can be observed in the pressure range investigated. Using the data on the pure orthoenstatite as reference, we can confirm the basic influences of element substitutions on the evolution of the crystal structure with pressure.

The high-pressure behavior of bloedite: A synchrotron single-crystal X-ray diffraction study

Abstract High-pressure single-crystal synchrotron X-ray diffraction was carried out on a single crystal of bloedite [Na2Mg(SO4)24H2O] compressed in a diamond-anvil cell. The volume-pressure data, collected up to 11.2 GPa, were fitted by a second- and a third-order Birch-Murnaghan equation of state (EOS), yielding V0 = 495.6(7) Å3 with K0 = 39.9(6) GPa, and V0 = 496.9(7) Å3, with K0 = 36(1) GPa and K′ = 5.1 (4) GPa-1, respectively. The axial moduli were calculated using a Birch-Murnaghan EOS truncated at the second order, fixing K′ equal to 4, for a and b axes and a third-order Birch-Murnaghan EOS for c axis. The results were a0 = 11.08(1) and K0 = 56(3) GPa, b0 = 8.20(2) and K0 = 43(3) GPa, and c0 = 5.528(5), K0 = 40(2) GPa, K′ = 1.7(3) GPa-1. The values of the compressibility for a, b, and c axes are βa = 0.0060(3) GPa-1, βb = 0.0078(5) GPa-1, βc = 0.0083(4) GPa-1 with an anisotropic ratio of βa:βb:βc = 0.72:0.94:1. The evolution of crystal lattice and geometrical parameters indicates no phase transition up to 11 GPa. Sulfate polyhedra are incompressible, whereas the Mg polyhedral bulk modulus is 95 GPa. The sodium polyhedron is the softest part of the whole structure with a bulk modulus of 41 GPa. Pressure decreases significantly the distortion of Na coordination. Up to 10 GPa, the donor-acceptor oxygen distances decrease significantly and the difference between the two water molecules decreases with an increase in the strengths of hydrogen bonds. At the same time, the bond lengths from Na and Mg to O atoms of the water molecules decrease faster than other bonds to these cations suggesting that there is a coupling between the Na-Ow and Mg-Ow bond strengths and the “hydrogen transfer” to acceptor O atoms.

Full analysis of feldspar texture and crystal structure by combining X-ray and electron techniques

Abstract Feldspar crystals typically show a range of exsolution and polysynthetic twinning textures that can present problems for their full characterization, but at the same time give important information about their genesis. We present an integrated procedure for the micro-texture analysis, twin law identification plus crystal structure refinement of all components in a feldspar intergrowth. This procedure was applied to perthitic intergrowths in feldspars from two different pegmatites in the Larvik plutonic complex in the southern part of the Oslo region, Norway. It revealed that the two starting high-temperature (HT) feldspars had similar global chemical compositions but underwent significantly different cooling histories, with cooling times probably differing by over an order of magnitude. Powder X-ray diffraction with Rietveld refinement was used for a preliminary identification of the mineral components and concluding quantitative phase analysis. Electron microprobe analysis was used to bracket the chemical compositions of the constituents. Electron backscatter diffraction was used to reveal the texture of the samples, twin laws and spatial distribution and crystallographic orientation of the crystal domains. Single-grain X-ray diffraction recorded by an area detector was applied for a simultaneous integration of reflection intensities for all crystallographic domains with different orientations and severe diffraction overlaps. The crystal structures were refined using the program JANA2006 that allows a simultaneous calculation for structurally different components. Combined results of various methods helped improve accuracy and resolve ambiguities that arise from the application of a single technique. The approach is widely applicable to the study of mineral intergrowths and bridges an existing gap in the routinely accessible data on the structural characteristics of rock constituents.

Incorporation of REE into leucophanite: a compositional and structural study

Abstract The crystal structures of nine, and the chemical compositions of ten, natural samples of leucophanite, ideally NaCaBeSi2O6F, were investigated. The analysed samples display a large compositional variation with trace-element abundances >50,000 ppm, primarily due to rare earth elements (REE). Fromthese data, we propose a substitution scheme for the incorporation of REE for Ca, with additional Na substituting for Ca and the generation of vacancies to ensure charge balance. Compositional zonation was observed in some samples; this zonation correlates with variations in cathodoluminescence. The crystal structure of the nine analysed samples could all be refined in space group P212121. We found no evidence for a reduction of symmetry with increased trace-element concentration. Various twin combinations were observed and these seem related to crystallization conditions rather than structural or chemical factors.

Metal transport and remobilisation in a basin affected by acid mine drainage: the role of ochreous amorphous precipitates

Metal-polluted mine waters represent a major threat to the quality of waters and sediments in a downstream basin. At the confluence between acidic mine waters and the unpolluted waters of the Gromolo Torrent (Liguria, North-West Italy), the massive formation of an ochreous amorphous precipitate takes place. This precipitate forms a soft blanket that covers the torrent bed and can be observed down to its mouth in the sea. The aim of this work is to evaluate the dispersion of metals in the Gromolo Torrent basin from the abandoned Cu-Fe sulphide mine of Libiola to the Ligurian Sea and to assess the metal remobilisation from the amorphous precipitates. The mineralogy of the superficial sediments collected in the torrent bed and the concentrations of different elements of environmental concern (Cu, Zn, Cd, Co, Cr, Mn, Ni, Pb, As, and Sb) were therefore analysed. The results showed that the precipitates contain high concentration of Fe, Al, Cu, and Zn, significantly modifying the bulk chemistry of the Gromolo Torrent sediments. In order to evaluate the possible remobilisation of ecotoxic elements from the amorphous precipitates, bulk leaching tests were performed with both deionised and seawater. Bulk leaching tests with deionised water mobilised primarily high Pb amounts, but also relatively high concentrations of Fe, Al, Cu, and Zn are released in the leachate. In seawater tests, Fe, Al, Cu, and Zn were released in smaller amounts, while other elements like Mn, Cd, Co, and Ni increased in the released fraction. Pb was still strongly released as in deionised water experiments. The results show that the interaction of precipitates and seawater can remobilise high concentrations of metals, thus affecting the surrounding environment.

The crystal structure of balićžunićite, Bi2O(SO4)2, a new natural bismuth oxide sulfate

Abstract The crystal structure of balićžunićite, Bi2O(SO4)2, a new mineral species from the La Fossa crater of Vulcano (Aeolian Islands, Italy), was solved from single-crystal X-ray diffraction data and refined to R = 0.0507. The structure is triclinic, space group P1̅., with a = 6.7386(3), b = 11.1844(5), c = 14.1754(7)Å , α = 80.082(2), β = 88.462(2)°, γ = 89.517(2)°, V = 1052.01(8) Å3 and Z = 6. The crystal structure consists of six independent Bi sites, six S sites and 27 O sites of which three are oxo oxygen atoms not bonded to sulfur. Bismuth and S atoms are arranged close to a eutectic pattern parallel to the (100) plane. The planes are stacked atom on atom such that Bi always overlays S and vice versa. This structural feature is shared with the known structure of the high-temperature polymorph of the same compound, stable at T >535°C. However, the sequences of Bi and S atoms in the two structures are different and so are the arrangements of oxygen atoms. Characteristic building blocks in the structure of balićžunićite are clusters of five Bi atoms which form nearly planar trapezoidal Bi5 groups with oxo oxygens located in the centres of the three Bi3 triangles, which form the trapezoids. The trapezoidal Bi5O39+ ions are joined along [100] with SO42- groups by means of strong bismuth-sulfate oxygen bonds, forming infinite [100] rods with composition Bi5O3(SO4)5-. One sixth of the Bi atoms do not participate in trapezoids, but form, with additional SO42- groups, rows of composition BiSO4+ also parallel to [100]. [Bi5O3(SO4)5-] rods form infinite layers parallel to (010) with [BiSO4+] rows located on the irregular surface of contact between adjacent layers. Bi atoms occur in four different coordination types, all showing the stereochemical influence of the Bi3+ lone electron pair. In this respect the crystal structure of balićžunićite shows greater variability than its high-temperature polymorph which has only two types of the Bi coordination spheres present in balićžunićite.

Crystal structure of (Bi 0.94 Sb 1.06 )S 3 and reconsideration of cation distribution over mixed sites in the bismuthinite- stibnite solid-solution series

The intermediate member of the (Bi,Sb)2S3 solid-solution series was prepared by dry synthesis at low temperature (200 °C) with a long annealing period in sealed silica tube. The EDS analysis yielded an empirical formula (Bi0.96Sb1.04)S3, which is very close to the formula (Bi0.94Sb1.06)S3 obtained by crystal structure analysis. The crystal structure was refined to the R-factors: R1 = 0.0288 for I > 2 s (I) and wR2 = 0.0542 for all data. (Bi0.94Sb1.06)S3 has orthorhombic symmetry with space group Pnma (No. 62). The asymmetric unit contains two independent mixed cation sites, both coordinated to seven S atoms in a form of mono- capped trigonal prism. They combine into infinite (M 4S6)n rods parallel to the (010) direction with only weak interactions between rods where the lone electron pairs are directed. Our data and the revaluation of previous data resolve a controversy about the distribution of Sb and Bi over the two structural sites which exists in previously published works. It is shown that the structural constraints favour a slight preference of the larger cation for the marginal M1 site over the whole span of the solid-solution series. The unit cell parameters show a deviation form the Vegards law connected with different rates of the parallel increase of lengths of the strong bonds and the decreasing influence of the lone electron pair with the replacement of Sb by Bi. The changes in the char - acter of the two independent cation sites introduced by this replacement are similar to those produced during compression of Sb2S3.