The rare potassium zirconium silicate dalyite has been identified for the first time on Terceira, Azores, within syenitic ejecta of the Caldeira-Castelinho Ignimbrite Formation. New quantitative analyses of this dalyite were combined with the small number of published analyses from various locations worldwide to evaluate the mineral's compositional variability. Additionally, solid-state modelling has been applied to assess the site allocations of substituting elements. The new analyses yield the average formula (K1.84Na0.15)∑=1.99(Zr0.94Ti0.012Hf0.011Fe0.004)∑=0.967Si6.03O15. Model results predict the placement of substituting Hf and Ti in the octahedral site, and highlight the overall complexity in the incorporation of Fe, Mg and Ba. The combined dataset reveals that dalyite found within peralkaline granites and syenites is generally defined by higher Na↔K substitution and lower Ti↔Zr substitution relative to dalyite from highly potassic rocks. The Terceira dalyite exhibits a bimodal variation in the degree of Na↔K substitution which is attributed to a K-enrichment trend induced by late-stage pore wall crystallization and albitization, coupled with the control of pore size upon the degree of supersaturation required to initiate nucleation of dalyite in pores of varying size.

Optical microscopy, Raman spectroscopy and electron probe microanalyses were conducted on a migmatitic metapelite to investigate the effects of alpha radiation and subsequent alteration at the interface between uraninite inclusions and the host minerals biotite, chlorite and albitic plagioclase. The study reveals (1) anomalous colouration under the polarizing microscope; (2) pertinent changes in the characteristic Raman spectra of host phases; (3) reaction aureoles, composed of secondary phases (viz. chlorite and K-feldspar) of various sizes (∼15–45 μm) within biotite and plagioclase, respectively; (iv) K-feldspatization and sericitization of plagioclase at the grain boundaries; (5) agreement between the observed α-penetration depths and the Monte-Carlo simulation results; and (6) dissolution textures within the matrix monazites. Analysis of the compositions of the reaction aureoles in albitic plagioclase reveals a systematic distribution of K-feldspar-, LREE- and clay-rich zones; while the same in biotite is composed of secondary chlorite. The growth sequence of the secondary phases indicates an influx of a K-rich fluid, following intense radiation damage, efficiently superimposed by LREE-metasomatism and later acidic alteration. These changes took place under low-temperature (≤150°C) conditions, wherein radial cracks (within plagioclase) and cleavages/fractures (within biotite) favoured fluid infiltration-circulation into the reaction aureoles. Depletion of the LREEs from the dissolved matrix monazites and their enrichment as a discrete LREE phase within the damaged aureoles in plagioclase demonstrate micrometre-scale LREE mobility.

The geology of the 2.7 Ga Stillwater Complex in South-Central Montana is reviewed with a focus on the role of volatiles in locally modifying both the crystallization sequence of the evolving parent magma and the initially precipitated solid assemblages to favour olivine ± chromite. A secondary origin for these two minerals is particularly probable for the olivine-bearing rocks of the Banded series and, at a minimum, also increasing their modal abundance in the Peridotite zone of the Ultramafic series. Direct evidence for volatiles includes the presence of high-temperature fluid inclusions in pegmatoids and hydrous melt inclusions (now crystallized) in chromite and olivine from both the Ultramafic and the Banded series rocks. Indirect evidence includes the boninitic character of the parent magma, the presence of volatile-bearing minerals including high-temperature carbonates, rock textures, and Cl / F variations in apatite. Mechanisms which favour the formation of olivine (± chromite) over pyroxene include volatile phase boundary shifts induced by added H2O, incongruent melting of pyroxene by hydration of a partly-molten mush, and the near- to sub-solidus replacement of pyroxene by olivine and chromite by silica-undersaturated fluids. These mechanisms cast doubt that magmas with different liquid lines of descent were involved in the crystallization of the Stillwater Complex. A dry Stillwater magma would have been mineralogically and modally much less varied and lacking in high-grade platinum-group element and chromium deposits.

A new mineral katiarsite, ideally KTiO(AsO4), occurs in sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with hatertite, bradaczekite, johillerite, yurmarinite, tilasite, arsmirandite, hematite, tenorite, As-bearing orthoclase, fluorophlogopite and aphthitalite. Katiarsite occurs as long prismatic to acicular, typically sword-like, crystals up to 3 μm×10μm×50 μm in size, and rarely up to 0.15 mm long. Crystal forms are {011}, {201}, {100} and {001}. Katiarsite is transparent, colourless, with a vitreous lustre. The mineral is brittle. Cleavage was not observed, the fracture is uneven. Dcalc is 3.49 g cm–3. Katiarsite is optically biaxial (+), α = 1.784(3), β = 1.792(3), γ = 1.870(5); 2Vobs is small. Orientation is X = b, Y = a, Z = c. The Raman spectrum is reported. The chemical composition (wt.%, electron-microprobe data) is K2O 18.98, Fe2O3 5.07, TiO2 27.49, As2O5 47.48, total 99.02. The empirical formula, calculated based on 5 O apfu, is K1.00 (Ti0.85Fe3+0.16)∑1.01 As1.02O5. The strongest reflections of the powder X-ray diffraction pattern [d,Å(I)(hkl)] are 5.91(17)(110), 5.62(74)(011), 4.18(19)(202), 3.157(66) (013), 2.826(100)(221), 2.809(96)(022) and 2.704(19)(004). Katiarsite is orthorhombic, a = 13.174(4), b = 6.5635(10), c = 10.805(2) Å, V = 934.3(3) Å3, Z = 8, space group Pna21, by analogy with KTA, synthetic KTiO(AsO4), a notable non-linear optical crystalline material. The name of the mineral reflects its chemical composition, kalium titanyl arsenate.

The new mineral tavagnascoite, Bi4O4 (SO4)(OH)2, was discovered in the Pb-Bi-Zn-As-Fe-Cu ore district of Tavagnasco, Turin, Piedmont, Italy. It occurs as blocky, colourless crystals, up to 40 μm in size, with a silky lustre. In the specimen studied, tavagnascoite is associated with other uncharacterized secondary Bi-minerals originating from the alteration of a bismuthinite ± Bi-sulfosalt assemblage. Electron microprobe analyses gave (average of three spot analyses, wt.%) Bi2O3 85.32, Sb2O3 0.58, PbO 2.18, SO3 8.46, H2Ocalc 1.77, sum 98.31. On the basis of 10 O apfu, the chemical formula is (Bi3.74Pb0.10Sb0.04)∑ = 3.88O3.68 (SO4)1.08(OH)2, with rounding errors. Main calculated diffraction lines are [d in Å (relative intensity) hkl] 6.39 (29) 012, 4.95 (19) 111,4.019(32)121,3.604(28)014 and 3.213(100)123. Unit-cell parameters are a = 5.831(1), b = 11.925(2), c = 15.123(1) Å, V = 1051.6(3) Å3, Z = 4, space group Pca21. The crystal structure was solved and refined from single-crystal X-ray diffraction data to R 1 = 0.037 on the basis of 1269 observed reflections. It consists of Bi–O polyhedra and SO4 tetrahedra. Bismuth polyhedra are connected each to other to form Bi–O sheets parallel to (001). Successive sheets are linked together by SO4 groups and hydrogen bonds. Tavagnascoite is the Bi-analogue of klebelsbergite, Sb4O4(SO4)(OH)2, and it is the fifth natural known bismuth sulfate without additional cations. The mineral and its name have been approved by the IMA CNMNC (2014-099).

We describe the structures and transformations that lead to the crystallization of a post-post-perovskite of Sb2S3 type in a GdFeO3-type fluoroperovskite system at high-pressure conditions, through use of large-volume powder and single-crystal x-ray diffraction techniques. The results of this analysis gives unique access to the relative crystallographic orientations of all the polymorphs encountered (GdFeO3 type, CaIrO3 type and Sb2S3 type). We use this information to extend this description to include other calculated and observed forms that are competitive in ABX3 and A2X3 stoichiometries (e.g. α-Gd2S3 and Be3N2 types) and provide substantial information on inter-relationships between these structures. Such information is critical to the interpretation of transition mechanisms, predicting transition sequences and to the expression of directional properties in those transformed structures. The transformation from CaIrO3 type to Sb2S3 type is group-subgroup, from Cmcm with fc2a, to Pnma c5, with no observable volume change, but considerable change to the morphology of the lattice. There is a concomitant increase in coordination and average bond length compared to the post-perovskite form of NaFeF3.

The new mineral species meerschautite, ideally (Ag,Cu)5.5Pb42.4(Sb,As)45.1S112O0.8, has been discovered in the baryte + pyrite ± (Pb-Zn-Ag) deposit of the Pollone mine, near Valdicastello Carducci, Apuan Alps, Tuscany, Italy. It occurs as black prismatic crystals, striated along [100], up to 2 mm long and 0.5 mm thick, associated with baryte, boulangerite, pyrite, quartz and sphalerite. Meerschautite is opaque with a metallic lustre and shows a black streak. In reflected light, meerschautite is white in colour, weakly bireflectant and non pleochroic. With crossed polars, it is distinctly anisotropic with grey to dark grey rotation tints with brownish and greenish shades. Reflectance percentages for COM wavelengths [λ (nm), Rair (%)] are: 470: 39.7/41.4; 546: 38.3/39.9; 589: 37.4/39.0; 650: 35.8/37.2. Electron-microprobe data collected on two different samples gave (wt.%): Cu 0.22, Ag 3.15, Tl 0.07, Pb 48.54, Sb 25.41, As 2.82, S 19.74, Se 0.14, Cl 0.03, sum 100.12 (# 1) and Cu 0.22, Ag 3.04, Tl 0.13, Pb 48.53, Sb 25.40, As 2.93, Bi 0.06, S 19.82, Se 0.13, Cl 0.05, sum 100.31 (# 2). On the basis of 112 anions (S+Se+Cl) per formula unit, the empirical formulae are (Ag5.29Cu0.63)∑5.92(Pb42.43Tl0.06)∑42.49(Sb37.80As6.82)∑44.62(S111.53Se0.32Cl0.15)∑112 (# 1) and (Ag5.08Cu0.62)∑5.70(Pb42.22Tl0.12)∑42.34(Sb37.61As7.07Bi0.05)∑44.73(S111.45Se0.30Cl0.25)∑112 (# 2). Main diffraction lines, corresponding to multiple hkl indices, are [d in Å (relative visual intensity)]: 3.762 (m), 3.663 (s), 3.334 (vs), 3.244 (s), 3.016 (m), 2.968 (m), 2.902 (m), 2.072 (ms). The crystal structure study gave a monoclinic unit cell, space group P21, with a = 8.2393(1), b = 43.6015(13), c = 28.3688(8) Å, β = 94.128(2)°, V = 10164.93(2) Å3, Z = 2. The crystal structure has been solved and refined to a final R1 = 0.122 on the basis of 49,037 observed reflections. The structure is based on two building blocks, both formed by a complex column with a pseudotrigonal Pb6S12 core and two arms of unequal lengths (short and long arms, respectively). Two different kinds of short arms occur in meerschautite. One is an Ag-rich arm, whereas the other shows localized Sb–O–Sb bonds. Meerschautite is an expanded derivative of owyheeite and has quasi-homeotypic relationships with sterryite and parasterryite.