Tonci Balic-Zunic

Crystal structure analyses of four tourmaline specimens from the Cleopatra’s Mines (Egypt) and Jabal Zalm (Saudi Arabia), and the role of Al in the tourmaline group

Abstract Fe-rich “oxydravite” and dravite from the Late Proterozoic ophiolitic mélange of the Arabo-Nubian Shield, located in Egypt and Saudi Arabia, were structurally and chemically characterized by using crystal structure refinement based on single-crystal X-ray diffraction data, electron microprobe analysis, and Mössbauer spectroscopy. Structural formulae obtained by optimization procedures indicate disordering of Al, Mg, and Fe2+ over the Y and Z sites, and an ordering of Fe3+ at Y. The disordering can be explained by the substitution mechanisms 2YMg+ZAl+WOH = 2YAl+ZMg+WO2- and 2YFe2++ZFe3++WOH = 2YFe3++ZFe2++WO2-, which are consistent with reducing the mismatch in dimensions between YO6 and ZO6 octahedra. To explain the Mg-Al disordering process, as well as the occurrence of B at the T site in tourmaline, analogies have been drawn between the crystal structure of tourmaline and that of lizardite. A critical constraint in both structures is the geometrical fit of the six-membered tetrahedral ring with the attached group of three YO6 octahedra. In tourmaline, the disordering of Mg and Al over Y and Z relieves the strain due to the misfit in dimensions of the larger triads of edge-sharing MgO6 octahedra and the smaller Si6O18 tetrahedral rings. In Al-rich tourmaline, where the octahedral cluster is smaller, the strain can be relieved by incorporating B in the tetrahedra. An opposite effect is observed by substitution of Al for Si at the tetrahedral site in Mg-rich tourmaline. Because the Al radius is intermediate between those of Mg and Si, Al plays an important structural role in accommodating the potential misfit between YO6, ZO6, and TO4 polyhedra. The amount of Al and its distribution in the structure strongly affects the values of the unit-cell parameters of tourmaline and yields volume variations according to a quadratic model. This results from the effect of ZAl combined with the occurrence of B at T in Al-rich tourmaline. ZAl has a greater effect than YAl as long as Al does not fully occupy the Z site.

Comparative compressibility and structural behavior of spinel MgAl2O4 at high pressures: The independency on the degree of cation order

Abstract The equation of state and the crystal structure evolution with pressure were determined for two single crystals of pure natural MgAl2O4 spinels with different degrees of order. The two samples studied were cut from a larger single crystal and one of them was experimentally disordered at high temperature. The two crystals, showing an inversion parameter x of 0.27 and 0.15 at ambient conditions, were loaded together in a diamond anvil cell and their unit-cell edge was measured up to about 7.5 GPa at 14 different pressures. The unit-cell volume, V0, the bulk modulus, KT0, and its first pressure derivative, K′, were simultaneously refined using a third-order Birch-Murnaghan equation of state, giving the following coefficients: V0 = 529.32(2) Å3, KT0 = 193(1) GPa, K′ = 5.6(3) for the ordered sample and V0 = 528.39(2) Å3, KT0 = 192(1) GPa, K′ = 5.4(3) for the disordered one. Complete intensity data were collected at 0, 0.44, 2.92, 7.34, and 8.03 GPa in a separate experiment. For the ordered and disordered samples the oxygen atomic coordinate u remains practically unchanged inside the investigated pressure range with an average value of 0.2633(5) and 0.2614(2), respectively. As a consequence, the polyhedral compressibilities are similar and are not influenced by the Mg/Al distribution over the two crystallographic sites. This also suggests that pressure has little or no influence on the degree of order in the MgAl2O4 spinel.

Time-response relationship of nano and micro particle induced lung inflammation. Quartz as reference compound

An increasing number of engineered particles, including nanoparticles, are being manufactured, increasing the need for simple low-dose toxicological screening methods. This study aimed to investigate the kinetics of biomarkers related to acute and sub-chronic particle-induced lung inflammation of quartz. Mice were intratracheal instilled with 50 µg of microsized or nanosized quartz. Acute inflammation was assessed 1, 2, 4, 8, 16 or 48 hours post exposure, whereas sub-chronic inflammation was investigated 3 months after exposure. Markers of acute inflammation in the bronchoalveolar lavage fluid (BALF) were neutrophils (PMN), tumor necrosis factor-alfa (TNF-α), interleukin (IL)-1β, macrophage inflammatory protein-2 (MIP-2), keratinocyte derived chemokine (KC) and total protein, which were all close to maximum 16 hours post instillation. No major differences were seen in the time-response profiles of nano- and micro-sized particles. The potency of the two samples cannot be compared; during the milling process, a substantial part of the quartz was converted to amorphous silica and contaminated with corundum. For screening, BALF PMN, either TNF-α or IL-1β at 16 hours post instillation may be useful. At 3 months post instillation, KC, PMN and macrophages were elevated. Histology showed no interstitial inflammation three months post instillation. For screening of sub-chronic effects, KC, PMN, macrophages and histopathology is considered sufficient.

Study of the temperature dependence of the structure of KY3F10

KY3F10 (Fmm, Z = 8) is an anion-excess fluorite-related superstructure, which is employed as a room-temperature laser, when doped with rare-earths. Earlier conductivity measurements have revealed two thermally activated processes below and above 600 K. In this work we studied the high-temperature behaviour of KY3F10 in the temperature range from 293 K up to 800 K at ambient pressure using x-ray powde ra nd single crystal diffraction. No structural phase transition is observed in this temperature range and the structure determinations reveal that the change of structural parameters, interatomic distances, and angles with temperature is very small. A prominent maximum observed in the difference Fourier maps, which corresponds to the centre of an empty F8 cube, might be one of the interstitial sites involved in the conduction mechanism.

High-pressure anisotropic distortion of Pb3Bi2S6: a pressure-induced, reversible phase transition with migration of chemical bonds.

The compound Pb 3Bi 2S 6 is investigated by X-ray diffraction on single crystals in a diamond-anvil cell between 0.0001 and 10.5 GPa. It undergoes a first-order phase transition at hydrostatic pressure between 3.7 and 4.9 GPa. The space group symmetry changes from Bbmm to Pbnm, and the unit-cell volume decreases by 4%. The transition is strongly anisotropic, with a contraction along one of the crystal axes by 16% and expansion along another one by 14%. This is a piezoplastic phase transition, a displacive pressure-induced phase transition with systematic shearing of atomic planes and a migration of chemical bonds in the structure. In the case of Pb 3Bi 2S 6 the transition is achieved by the change of the archetypal architecture of the structure-building modules from a PbS-like to a SnS-like arrangement and a loss of mirror planes on the contact surfaces of modules. The phase transition is reversible with a preservation of the single crystal, which is a result of the stereochemical influence and migration of the s (2) lone electron pairs of Pb (II) and Bi (III).

Identification of monoclinic calcium pyrophosphate dihydrate and hydroxyapatite in human sclera using Raman microspectroscopy.

Raman microspectroscopy was first used to determine the composition of a calcified plaque located at the pterygium‐excision site of a 51‐year‐old female patient’s left nasal sclera after surgery. It was unexpectedly found that the Raman spectrum of the calcified sample at 1149, 1108, 1049, 756, 517, 376 and 352/cm was similar to the Raman spectrum of monoclinic form of calcium pyrophosphate dihydrate (CPPD) crystal, but differed from the Raman spectrum of triclinic form of CPPD. An additional peak at 958/cm was also observed in the Raman spectrum of the calcified plaque, which was identical to the characteristic peak at 958/cm of hydroxyapatite (HA). This is the first study to report the spectral biodiagnosis of both monoclinic CPPD and HA co‐deposited in the calcified plaque of a patient with sclera dystrophic calcification using Raman microspectroscopy.

The crystal structure of vurroite, Pb20Sn2(Bi, As)22S54Cl6: OD-character, polytypism, twinning, and modular description

Abstract The crystal structure of the type specimen of vurroite from Vulcano (Aeolian Islands, Italy) has been solved and refined using single-crystal X-ray diffraction data collected at the Elettra synchrotron facility (Basovizza, Trieste). Vurroite has an OD (order-disorder) structure belonging to the category III of OD structures composed of equivalent layers. The OD-groupoid family (λ and σ partial operations) and MDO structures were derived by means of the application of the OD theory. The two theoretically possible polytypes with maximum degree of order (MDO polytypes) have pseudo-orthorhombic metric, with lattice parameters a ≈ 45.6, b ≈ 8.4, c ≈ 54 Å, and a ≈ 22.8, b ≈ 8.4, c ≈ 54 Å, and space group symmetries F2/d11 and A2/d11, respectively. Only the former polytype (MDO1) could be identified in the analyzed crystals. The MDO1 structure was solved and refined to R = 6.26% for 4968 reflections with Fo > 4σ(Fo). In the standard C2/c setting of the space group the unit-cell parameters of MDO1 are a = 8.371(2), b = 45.502(9), c = 27.273(6) Å, β = 98.83(3)°, V = 10265(4) Å3, Z = 4. Frequent twinning with (001) as the twin plane, together with the occurrence of disordered domains in the structure, was observed. The crystal structure of vurroite contains lozenge-shaped composite rods made of coordination polyhedra of Pb and Sn, interconnected into layers parallel to (010) of the standard monoclinic setting. These layers are separated by ribbons of As and Bi, each in distorted octahedral coordination. The ribbons form wavy, discontinuous double layers of PbS archetype. Lone electron pairs of As and Bi are accommodated in the central portions of the PbS-like layers. The structure of vurroite contains building blocks topologically similar to those found in the zinckenite group and in the structure of kirkiite. It can be considered a box-work structure containing the smallest possible pseudo-hexagonal block in the form of a sole octahedron.

Comparison between beryllium and diamond-backing plates in diamond-anvil cells: Application to single-crystal x-ray diffraction high-pressure data

A direct comparison between two complete intensity datasets, collected on the same sample loaded in two identical diamond-anvil pressure cells equipped, respectively, with beryllium and diamond-backing plates was performed. The results clearly demonstrate that the use of diamond-backing plates significantly improves the quality of crystal structure data. There is a decrease in the internal R factor for averaging, structure refinement agreement factors, and in the errors and uncertainties of the atomic coordinates, atomic displacement parameters, and individual bond lengths.

First occurrence of iodine in natural sulfosalts : The case of mutnovskite, Pb2AsS3(I,Cl,Br), a new mineral from the Mutnovsky volcano, Kamchatka Peninsula, Russian Federation

Abstract Mutnovskite, ideally Pb2AsS3(I,Cl,Br), is a new mineral from the high-temperature fumaroles of the Mutnovsky volcano, Kamchatka Peninsula, Russian Federation. It occurs as microscopic rubycolored short-prismatic crystals up to 100 μm across, closely associated with halogen-sulfosalts of Pb, Bi, and As, Cd-Pb-Bi sulfosalts, pyrite, anhydrite, and cristobalite. Mutnovskite is transparent in thin fragments with a dark-red to blue color. The crystals are soft and fragile. Cleavage and fracture were not observed and the Mohs hardness is approximately 2. In reflected light mutnovskite is silvery lead-grey in color with an iridescent tarnish. Pleochroism and anisotropy are not visible because of the strong orange internal reflections, especially in immersion. Reflectance percentages measured in air in the range 400.700 nm were tabulated. Reflectance percentages (Rmin and Rmax) for the four COM wavelengths are 34.2, 34.6 (470 nm), 33.2, 33.5 (546 nm), 32.5, 32.7 (589 nm), and 31.4, 31.7 (650 nm), respectively. A mean of four electron microprobe analyses gave Pb 62.0(3), As 11.0(4), Bi 0.6(1), S 14.4(2), Se 0.2(3), I 8.9(3), Cl 2.44(9), Br 1.1(7), Cu 0.03(2), Fe 0.01(1), total 100.7 wt%, corresponding, on the basis of a total of 7 atoms, to Pb1.99(As0.98Bi0.02)Σ1.00(S2.98Se0.02)Σ3.00(I0.47Cl0.46Br0.09)Σ1.02. The nine strongest powder-diffraction lines [d in Å (I/I0) (hkl)] are: 4.69 (32) (002); 4.37 (67) (210); 3.34 (73) (020); 3.19 (100) (212); 2.715 (61) (022); 2.648 (66) (410); 2.539 (31) (213); 2.455 (29) (402); 1.894 (30) (232). Mutnovskite is orthorhombic, space group Pnma, with a = 11.543(1), b = 6.6764(7), and c = 9.359(1) Å, V = 721.3(1) Å3, Z = 4. The crystal structure was solved and refined to R = 4.14%. It consists of three independent cation positions: Pb1 and Pb2 have tricapped trigonal prismatic coordinations with S and I atoms (completed with one As atom in the case of Pb2), while As has threefold coordination with S atoms, which form the base of a trigonal pyramid with As at the apex. Pairs of Pb1-Pb2 prisms are connected in columns which extend along c. AsS3 coordinations are isolated from each other. S atoms and half of the Pb atoms form wavy close-packed layers. Two kinds of channels parallel to boccur between the layers. The smaller channels host As atoms close to the channel walls, with their lone-electron pairs occupying the median part, while the bigger ones accommodate rows of alternating halogen and Pb atoms. The new mineral is named after the type locality, the Mutnovsky volcano, Kamchatka Peninsula, Russian Federation.

First occurrence of close-to-ideal kirkiite at Vulcano (Aeolian Islands, Italy) : chemical data and single-crystal X-ray study

Samples of kirkiite from the high temperature fumaroles of La Fossa crater of Vulcano (Aeolian islands, Italy) were chemically and structurally investigated in this work. Associated minerals are vurroite, bismuthinite, galenobismutite, cannizzarite, lillianite, heyrovskýite, galena, and other less characterized Pb(Bi)-sulfochlorides. Electron-microprobe analyses gave the average chemical formula Pb 10.00 Bi 3.01 As 3.01 (S 18.47 Se 0.44 C 10.06 ) which is very close to the ideal composition of kirkiite, Pb 10 Bi 3 As 3 S 19 , and indeed significantly closer than the composition of the type specimen, Pb 10.08 Bi 2.55 Sb 0.13 As 2.91 S 19 . Lattice parameters are: a = 8.700(2) A, β = 26.237(6) A, c = 8.774(3) A, β = 119.653(4)°, V = 1740.2(9) A 3 . A twinned structure was refined using single-crystal data (Mo K α X-ray diffraction, CCD detector). The refinement converges to R = 0.074 for 1443 reflections with F 0 > 4σ(F 0 ). The structure of the close-to-ideal kirkiite from Vulcano has been compared with the structure of the type specimen. The comparison reveals a variation in As-Bi substitution, with samples from Vulcano probably being close to the maximum possible Bi and the minimum As content for this structure type. This is reflected in more regular and symmetric coordination polyhedra than in the holotype, as well as in the overall regularity of the structure. The increased Bi:As ratio produces an elongation of the a and b lattice periods, and a shortening of the c period, and increases the frequency of twinning in kirkiite.