Two-dimensional nets may be used to generate the stoichiometry and structure of single-layer and double-layer sheet-silicate minerals. Many sheet-silicate minerals are based on the 3-connected plane nets 63, 4.82, (4.6.8)2(6.82)1and (52.8)1(5.82)1, and some more complicated nets, e.g. (5.6.7)4(5.72)1(62.7)1, (4.122)2(42.12)1, (52.8)1(5.62)1(5.6.8)2(62.8)1,have one or two representative structures. Many complicated sheet-silicate minerals are based on sheets of 2-, 3- and 4-connected tetrahedra that may be developed from 3- and 4-connected plane nets by a series of oikodoméic operations on 3- or 4-connected nets that change the topologyof the parent net. There are three classes of oikodoméic operations: (1) insertion of 2- and 3-connected vertices into 3- and 4-connected plane nets; (2,3) replication of single-layer sheets by topological mirror or two-fold-rotation operators, and condensation of the resulting twosingle-layer sheets to form double-layer sheets. The topological aspects of these sheet structures may be described by functions that express stoichiometry in terms of tetrahedron connectivities (formula-generating functions) and functions that associate these formula-generating functionswith specific two-dimensional nets. Using these functions, we may generate formulae and structural arrangements of single-layer and double-layer silicate structures with specific local and long-range topological features.

Macro- and micro-perthitic microclines from pegmatites from Perth, Ontario (Wards catalogue 46 E 0510) and Keystone, South Dakota (Wards 46 E 5125) have been studied using light and electron microscopy. A sample of the type perthite from Perth, Ontario (Hunterian Museum, Glasgow, M2361)was compared using light microscopy. It differs in bulk composition and microtexture from the Wards sample. The Perth sample from Wards is a mesoperthite, with sub-periodic ∼mm-thick albite veins near (100), with irregular surfaces. The microcline has regular tartan twins and formed fromorthoclase by a continuous process. The Keystone sample is a microperthite, with non-periodic albite veins mainly in {110}. Irregular tartan twins, volumes of irregular microcline and subgrains suggest that the microcline formed by dissolution–reprecipitation. Microcline in both samplescontains semicoherent cryptoperthitic albite films that formed after the development of tartan twins. The bulk compositions of these intergrowths imply exsolution below ∼400°C. Diffusion parameters imply sustained heating for between 0.11 My at 400°C, 1.5 GPa and 8.4 My at 300°C,1 GPa. Unrealistic times are required at 200°C. Subsequently, the crystals reacted with a fluid leading to replacive growth of the vein perthites. Unusually, Albite twin composition planes in replacive subgrains have sub-periodic dislocations, formed by coalescence of advancing growthtwins. Processes that might lead to periodic, replacive intergrowths are discussed. The Perth and Keystone feldspars have been used for experimental work on dissolution during weathering and on anomalous thermoluminescence fading. Their microtextures make them unsuitable for obtaining propertiesthat can be extrapolated to feldspars in general.

Two new minerals shchurovskyite, ideally K2CaCu6O2(AsO4)4, and dmisokolovite, ideally K3Cu5AlO2(AsO4)4, are found in sublimates of the Arsenatnaya fumarole at the Second scoriacone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka Peninsula, Russia. They are associated with one another and with johillerite, bradaczekite, tilasite, melanarsite, tenorite, hematite, aphthitalite, langbeinite, orthoclase, etc. Shchurovskyiteoccurs as coarse tabular or prismatic crystals up to 0.15 mm in size or anhedral grains forming parallel aggregates and crusts up to 1.5 cm × 2 cm across. Dmisokolovite forms tabular, prismatic or dipyramidal crystals up to 0.2 mm in size, commonly combined in clusters or crusts up to0.7 cm × 1.5 cm across. Both minerals are transparent with a vitreous lustre. They are brittle, with Mohs' hardness ≈3. Shchurovskyite is olive-green or olive drab. Dmisokolovite is bright emerald-green to light green. Dcalc = 4.28 (shchurovskyite) and 4.26 (dmisokolovite)g cm–3. Both are optically biaxial; shchurovskyite: (+), α = 1.795(5), β = 1.800(5), γ = 1.810(6), 2Vmeas = 70(15)°; dmisokolovite: (–), α = 1.758(7), β = 1.782(7), γ = 1.805(8), 2Vmeas = 85(5)°. The Ramanspectra are given. Chemical data (wt.%, electron-microprobe; first value is for shchurovskyite, second for dmisokolovite): Na2O 0.00, 0.83; K2O 8.85, 10.71; Rb2O 0.11, 0.00; MgO 0.00, 0.35; CaO 4.94, 0.21; CuO 43.19, 38.67; ZnO 0.42, 0.20; Al2O30.04, 4.68; Fe2O3 0.00, 0.36; P2O5 0.59, 0.78; V2O5 0.01, 0.04; As2O5 40.72, 43.01; SO3 0.35, 0.00; total 99.22, 99.84. The empirical formulae, based on 18 O a.p.f.u., are shchurovskyite: K2.05Rb0.01Ca0.96Cu5.92Zn0.06Al0.01P0.09S0.05As3.86O18;dmisokolovite: Na0.28K2.36Mg0.09Ca0.04Cu5.04Zn0.04 Al0.95Fe0.053+P0.11As3.88O18. The strongest reflections of X-ray powder patterns [d,Å(I)(hkl)]are shchurovskyite: 8.61(100)(200, 001), 5.400(32)(110), 2.974(32)(312, 510), 2.842(47)(003, 020), 2.757(63) (601, 511), 2.373(36)(512, 420) and 2.297(31)(421, 222, 313); dmisokolovite: 8.34(95)(002), 5.433(84)(110), 2.921(66)(510, 314), 2.853(58)(511, 020) and 2.733(100)(006, 512, 602). Shchurovskyiteis monoclinic, C2, a = 17.2856(9), b = 5.6705(4), c = 8.5734(6) Å, β = 92.953(6)°, V = 839.24(9) Å3 and Z = 2. Dmisokolovite is monoclinic, C2/c, a = 17.0848(12), b = 5.7188(4), c =16.5332(12) Å, β = 91.716(6)°, V = 1614.7(2) Å3 and Z = 4. Their crystal structures [single-crystal X-ray diffraction data, R = 0.0746 (shchurovskyite) and 0.1345 (dmisokolovite: model)] are closely related in the topology of the main buildingunits. They are based on a quasi-framework consisting of AsO4 tetrahedra and polyhedra centred by Cu in shchurovskyite or by Cu and Al in dmisokolovite. K and Ca are located in channels of the quasi-framework. The minerals are named in honour of outstanding Russian geologists andmineralogists Grigory Efimovich Shchurovsky (1803–1884) and Dmitry Ivanovich Sokolov (1788–1852).

A multi-methodological study of the (K,Ca)-variety of the zeolite merlinoite from Fosso Attici, Sacrofano, Italy was carried out on the basis of electron microprobe analysis in wavelength dispersive mode, singlecrystal X-ray diffraction (at 100 K), Raman and infrared spectroscopy. Thechemical formula of the merlinoite from Fosso Attici is (Na0.37K5.69)Σ=6.06(Mg0.01Ca1.93Ba0.40)Σ=2.34(Fe0.023+Al10.55Si21.38)Σ=31.9O64·19.6H2O,compatible with the ideal chemical formula K6Ca2[Al10Si22O64]·20H2O.

Anisotropic structure refinements confirmed the symmetry and the framework model previously reported (space group Immm, a = 14.066(5),b = 14.111(5), c = 9.943(3) Å at 100 K). Refinement converged with four cationic sites and six H2O sites; refined bond distances of the framework tetrahedra suggest a highly disordered Si/Al-distribution. The Raman spectrum of merlinoite (collected between 100and 4000 cm–1) is dominated by a doublet of bands between 496–422 cm–1, assigned to tetrahedral T–O–T symmetric bending modes. T–O–T antisymmetric stretching is also observed; stretching and bending modes of the H2Omolecules are only clearly visible when using a blue laser. The single-crystal near-infrared spectrum shows a very weak band at 6823 cm–1, assigned to the first overtone of the O–H stretching mode, and a band at 5209 cm–1, due to the combination of H2Ostretching and bending modes. Avery broad and convoluted absorption, extending from 3700 to 3000 cm–1 occurs in the H2O stretching region, while the ν2 bending mode of H2O is found at 1649 cm–1. The powder mid-infraredspectrum of merlinoite between 400–1300 cm–1 is dominated by tetrahedral T–O–T symmetric and antisymmetric stretches. Raman and Fourier-transform infrared spectroscopy spectra of merlinoite and phillipsite provide a quick identification tool for these zeolites,which are often confused due to their close similarity.

A new silicate, colinowensite, BaCuSi2O6, has been found in the Wessels mine, Kalahari Manganese Field, South Africa. It is associated with effenbergerite, wesselsite, lavinskyite, scottyite, diegogattaite, as well as with pectolite, quartz, aegirine, richterite, minerals of the garnet group and a number of different manganese and iron oxides, especially hausmannite and hematite. The mineral was named for the mineral collector and finder of the new species, Colin R. Owens, of Somerset West, South Africa. Colinowensite is brittle, with uneven fracture, and the estimated Mohs hardness is ∼4. It occurs as subhedral crystals <100 μm in size. The forms {100} and {110} are observed while {001} is always present in cleavage plates. The calculated density is 4.236 g cm–3. It is the natural analogue of the synthetic pigmentreferred to as Chinese or Han purple, which is found on artifacts from ancient and imperial China. The mineral is of dark blue to purple colour, with a purple streak, and is uniaxial (–), with ω = 1.740 (20), ε = 1.735 (20) (420 nm) and ω = 1.745 (20), ε = 1.730(20) (650 nm). The lustre is vitreous and no fluorescence is observed under either shortwave or longwave ultraviolet radiation. Avery strong pleochroism occurs from purple along the c axis to blue in a perpendicular direction. Colinowensite is not soluble in acids except HF. Electron microprobe analyses gave an average composition (wt.%) of CuO 22.53, BaO 43.43 and SiO2 34.04 yielding the empirical formula (based on 6 O a.p.f.u.) BaCuSi2O6. The new mineral is tetragonal, space group I41/acd with Z = 16, anda = 9.967(1), c = 22.290 (2) Å. Colinowensite is a cyclosilicate with [Si4O12]8– 4-membered single rings, arranged in sheets parallel to (001). The structure is further characterized by CuO4 squares sharing corners with four neighbouring silicate rings within a sheet. Ba2+ cations are bonded to ten O atoms in irregular coordination. Average Si–O, Cu–O and Ba–O bond lengths are 1.619, 1.934 and 2.943 Å, respectively. Colinowensite belongs to subdivision 9. CE of the Strunz Mineralogical Tables. In addition, based on single-crystal X-ray work, new structural data for wesselsite of chemical composition Sr0.9Ba0.1CuSi4O10 are provided.

The first-principles plane-wave pseudopotential method is used to study the electronic and chemical structures of pyrite (FeS2) and arsenopyrite (FeAsS). The results indicate that an antibonding interaction occurs between Fe and As atoms in arsenopyrite. This interaction results in the Fe atom being repelled towards the S atom to stabilize antibonding orbitals, causing a larger S–Fe–S angle in arsenopyrite than in pyrite and a distortion in the arsenopyrite structure. In arsenopyrite, Fe–Fe distances are alternately long and short. The low spin density of the Fe d electrons supports this configuration in arsenopyrite. However, electron density calculations indicate that there is negligible electron density present between Fe atoms. This result indicates that cation-anion interactions are dominant in arsenopyrite. The pyrite Fe 3d orbital is split below the Fermi level, whereas the arsenopyrite Fe 3d orbital is not split, which can be attributed to the stronger interatomic bonding effects between Fe and S atoms in pyrite compared to arsenopyrite. It is found that the d-p orbital interactions between Fe and S atoms lead to bonding-antibonding splitting in both pyrite and arsenopyrite. However, the bonding effects between pyrite Fe and S atoms are stronger than in arsenopyrite. In arsenopyrite, the bonding interaction between the As 4p and Fe 3d orbitals is very weak, while the antibonding effect is very strong. The p-p orbital interaction is the dominant effect in As–S bonding. Frontier orbital calculations indicate that the Fermi levels of pyrite and arsenopyrite are notably close to each other, resulting in similar electrochemical activities. Orbital coefficient results show that the pyrite Fe 3d and S 3p orbitals are the active orbitals in the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), respectively. In the case of arsenopyrite, Fe 3d orbitals are very active in both the HOMO and LUMO. Moreover, the activity of the As 4p in the HOMO is greater than S 3p, whereas the opposite situation occurs in the LUMO. Based on these results, As atoms could be one of the active sites for the oxidation of arsenopyrite. In addition, separation of arsenopyrite and pyrite could be achieved by utilizing the difference in chemical reactivities of iron in the two minerals.

Bobshannonite, Na2KBa(Mn,Na)8(Nb,Ti)4(Si2O7)4O4(OH)4(O,F)2, is a new TS-block mineral from Mont Saint-Hilaire, Québec, Canada. It occurs as blocky crystals 0.5–1 mm across,perched on sérandite and albite. Other associated minerals are epididymite, catapleiite, aegirine, kupletskite, rhodochrosite and rhabdophane-(Ce). Bobshannonite occurs as vitreous to frosty, transparent to translucent very pale brown to orange brown crystals, has a very pale brown streak, hackly fracture and does not fluoresce under cathode or ultraviolet light. Cleavage is {001} very good, no parting was observed, Mohs hardness is ∼4, it is brittle and Dcalc. = 3.787 g/cm3. Crystals are twinned extensively and do not extinguish in cross-polarized light. Bobshannonite is triclinic, C1, a = 10.839(6), b = 13.912(8), c = 20.98(1) Å, α = 89.99(1), β = 95.05(2), γ = 89.998(9)°, V = 3152(5) Å3. The six strongest reflections in the powder X-ray diffraction data [d (Å),I, (hkl)] are: 2.873, 100, (241, 241, 044, 044, 241, 241); 3.477, 60, (006); 3.193, 59, (224, 224); 2.648, 40, (402, 243, 243); 2.608, 35, (008, 226, 226); 1.776, 30, (249). Chemical analysis by electron microprobe gave Ta2O5 0.52, Nb2O5 19.69,TiO2 5.50, SiO2 26.31, Al2O3 0.06, BaO 7.92, ZnO 1.02, FeO 0.89, MnO 26.34, MgO 0.06, Rb2O 0.42, K2O 2.38, Na2O 4.05, F 0.70, H2Ocalc. 1.96, O = –0.29, total 97.53 wt.%, where the H2O content was calculated from the crystal-structure analysis. The empirical formula on the basis of 38 anions is Na1.89(K0.93Rb0.08)Σ1.01Ba0.95(Mn6.85Na0.52Zn0.23Fe0.232+Mg0.03Al0.02)Σ7.88(Nb2.73Ti1.27Ta0.04)Σ4.04(Si8.07O28)O9.32H4.01F0.68,Z = 4. The crystal structure was refined to R1 = 2.55% on the basis of 7277 unique reflections [F > 4σ(F)] and can be described as a combination of a TS (Titanium Silicate) block and an I (Intermediate) block. The TS block consists ofHOH sheets (H – heteropolyhedral, O – octahedral). The topology of the TS block is as in Group II of the Ti disilicates: Ti + Nb = 2 a.p.f.u. per (Si2O7)2 [as defined by Sokolova (2006)]. In the O sheet, ten[6]MO sitesare occupied mainly by Mn, less Na and minor Zn, Fe2+, Mg and Al, with <MO–ϕ> = 2.223 Å. In the H sheet, four [6]MH sites are occupied by Nb and Ti (Nb > Ti), with <MH–ϕ> = 1.975 Å,and eight [4]Si sites are occupied by Si, with <Si–O> = 1.625 Å. The MH octahedra and Si2O7 groups constitute the H sheet. The TS blocks link via common vertices of MH octahedra. In the I block, Ba and Kare ordered at the AP(1) and AP(2) sites with Ba:K = 1:1 and the two BP sites are occupied by Na. The ideal composition of the I block is Na2KBa a.p.f.u. Bobshannonite, perraultite, surkhobite and jinshajiangite are topologically identical Group-II TS-block minerals. Bobshannonite is the Nb-analogue of perraultite. The mineral is named bobshannonite after Dr. Robert (Bob) D. Shannon (b. 1935), in recognition of his major contributions to the field of crystal chemistry in particular and mineralogy in general through his development of accurate and comprehensive ionic radii and his work on dielectric properties of minerals.

The phase equilibria in the system Ag–Pd–Te were studied by the technique of using an evacuated silica glass tube at 350° and 450°C. Five ternary phases were synthesized: sopcheite (Pd3Ag4Te4), lukkulaisvaaraite (Pd14Ag2Te9),telargpalite (Pd2–xAg1+xTe) and the previously unknown phases Pd7.5–xAg0.5+ xTe3 and Pd2+xAg2–xTe.The synthetic telargpalite has a compositional range from 26 to 29 wt.% Ag, with the formula Pd2–xAg1+xTe, where x varies from 0.09 to 0.22. The phase Pd2+xAg2–xTe has a compositional range from 34 to 35 wt.% Ag, where x varies from 0.18 to 0.24. The phase Pd7.5–xAg0.5+xTe3 forms a solid solution from 4 to 11 wt.% Ag, where x varies from 0.02 to 0.83. Phases Pd20Te7and Pd13Te3 dissolve up to 3.5 and 2 wt.% Ag, respectively. Other binary palladium tellurides do not dissolve Ag. The phase Pd3Ag4Te4, an analogue of the mineral sopcheite, forms a stable association with hessite and kotulskite it also coexists with lukkulaisvaaraite. Sopcheite is stable up to 383°C. Natural occurrences of hessite, kotulskite and lukkulaisvaaraite together in equilibrium indicate formation above this temperature. Phase relations defined the mineral assemblages that can be expected to occur in nature.The phase Pd7.5–xAg0.5+xTe3 potentially represents a new mineral; it will probably be found in association with lukkulaisvaaraite and telargpalite or telluropalladinite, among other platinum-group minerals. The phasePd2+xAg2–x Te can be found in association with telargpalite. Mineral assemblages defined in this study can be expected in Cu-Ni-PGE mineral deposits, associated with mafic and ultramafic igneous rocks, particularly in mineralized zones with known silver-palladium tellurides.

The oxidation state of Fe and precipitates within olivine phenocrysts from an olivine-basalt from Kuroshima volcano, Goto Islands, Nagasaki Prefecture, Japan, were determined using electron microprobe analysis, 57Fe Mössbauer spectroscopy, Raman spectroscopy and transmission electron microscopy, to examine the formation process of the Fe-bearing precipitates.

The average Fo content of the olivine phenocrysts is 76.2 mol.%. The olivine phenocrysts occasionally have precipitate minerals at their rims, especially on rims near vesicles. The 57Fe Mössbauer spectrum of olivine separates consists of two doublets assigned to Fe2+ at the octahedral M1 and M2 sites, and a Fe3+ doublet at the M1 and M2 sites. The Fe2+:Fe3+ ratio is 90(5):10(1). The precipitates at the rims of the olivine phenocrysts consistof magnetite and enstatite showing coaxial relations with host olivine, and grow parallel to the olivine c axis. Moreover, clusters consisting of nanoscale domains of a few tens of nm in size occur in the host olivine. Their rounded form and appearance in transmission electron microscope images are similar to those of the magnetite precipitates, but they have an olivine structure and can be regarded as embryos of magnetite within the olivine.

The oxidation process of olivine phenocrysts under cooling conditions is: (1) formation of magnetite embryos on the rims of olivinephenocrysts; (2) formation of enstatite-like pyroxene domains by depletion of Fe in olivine due to the generation of magnetite embryos; (3) crystallization of magnetite and enstatite-like pyroxene precipitates.

Bettertonite, ideally [Al6(AsO4)3(OH)9(H2O)5]·11H2O, is a new mineral from the Penberthy Croft mine, St. Hilary, Cornwall, England, UK. It occurs as tufts of white, ultrathin (sub-micrometre) rectangular laths, with lateral dimensions generally <20 μm. The laths are flattened on {010} and exhibit the forms {010}, {100} and {001}. The mineral is associated closely with arsenopyrite, chamosite, liskeardite, pharmacoalumite, pharmacosiderite and quartz. Bettertonite is translucent with a white streak and a vitreous to pearly, somewhat silky lustre. The calculated density is 2.02 g/cm3. Optically, bettertonite is biaxial positive with α = 1.511(1), β = 1.517(1), γ = 1.523(1) (in white light). The optical orientation is X = c, Y= b, Z = a. Pleochroism was not observed. Electron microprobe analyses (average of 4) with H2O calculated on structural grounds and analyses normalized to 100% gave Al2O3 = 29.5, Fe2O3 = 2.0, As2O5= 30.1, SO3 = 1.8, Cl = 0.5, H2O = 36.2. The empirical formula, based on 9 metal atoms is Al5.86Fe0.26(AsO4)2.65(SO4)0.23(OH)9.82Cl0.13(H2O)15.5. Bettertoniteis monoclinic, space group P21/c with unit-cell dimensions (100 K): a = 7.773(2), b = 26.991(5), c = 15.867(3) Å, β = 94.22(3)°. The strongest lines in the powder X-ray diffraction pattern are [dobs in Å(I)(hkl)] 13.648(100)(011); 13.505(50) (020); 7.805(50)(031); 7.461(30)(110); 5.880(20)(130); 3.589(20)(02); 2.857(14)(182). The structure of bettertonite was solved and refined to R1 = 0.083 for 2164 observed (I > 2σ(I)) reflections to a resolutionof 1 Å. Bettertonite has a heteropolyhedral layer structure, with the layers parallel to (010). The layers are strongly undulating and their stacking produces large channels along [100] that are filled with water molecules. The basic building block in the layers is a hexagonal ring ofedge-shared octahedra with an AsO4 tetrahedron attached to one side of the ring by corner-sharing. These polyoxometalate clusters, of composition [AsAl6O11(OH)9(H2O)5]8–, are interconnected along [100] and [001]by corner-sharing with other AsO4 tetrahedra.