Galena from four REE-rich (Khibina, Sallanlatvi, Seblyavr, Vuoriyarvi) and REE-poor (Kovdor) carbonatites, as well as hydrothermal veins (Khibina) all from the Devonian Kola Alkaline Province of northwestern Russia was analysed for trace elements and Pb and S isotope compositions. Microprobe analyses show that the only detectable elements in galena are Bi and Ag and these vary from not detectable to 2.23 and not detectable to 0.43 wt.% respectively. Three distinct galena groups can be recognized using Bi and Ag contents, which differ from groupings based on Pb isotope data. The Pb isotope ratios show significant spread with 206Pb/204Pb ratios (16.79 to 18.99), 207Pb/204Pb (15.22 to 15.58) and 208Pb/204Pb ratios (36.75 to 38.62). A near-linear array in a 207Pb/204Pb vs.206Pb/204Pb ratio diagram is consistent with mixing between distinct mantle sources, one of which formed during a major differentiation event in the late Archaean or earlier. The S isotopic composition (δ34S) of galena from carbonatites is significantly lighter (–6.7 to –10.3% Canyon Diablo Troilite (CDT) from REE-rich Khibina, Seblyavr and Vuoriyarvi carbonatites, and – 3.2% CDT from REE-poor Kovdor carbonatites) than the mantle value of 0%. Although there is no correlation between S and any of the Pb isotope ratios, Bi and Ag abundances correlate negatively with δ34S values. The variations in the isotopic composition of Pb are attributed to partial melting of an isotopically heterogeneous mantle source, while those of δ34S (together with Bi and Ag abundances) are considered to be process driven. Although variation in Pb isotope values between complexes might reflect different degrees of interaction between carbonatitic melts and continental crust or metasomatized lithosphere, the published noble gas and C, O, Sr, Nd and Hf isotopic data suggest that the variable Pb isotope ratios are best attributed to isotopic differences preserved within a sub-lithospheric mantle source. Different Pb isotopic compositions of galena from the same complex are consistent with a model of magma replenishment by carbonatitic melts/fluids each marked by quite different Pb isotopic compositions.

A new nomenclature scheme has been set up for the laueite supergroup of minerals, which have the general formula M12+M23+M33+(XO4)2(OH)2·8H2O, where M1 = Fe2+, Mg2+ or Mn2+; M2/M3 = Al3+ or Fe3+; and XO4 = PO4 or AsO4. The laueite supergroup is divided into the laueite group (XO4 = PO4) and the maghrebite group (XO4 = AsO4). These groups are then subdivided into subgroups on the basis of the dominant atoms, Al3+ or Fe3+, in octahedral sites M2/M3. The new nomenclature has been approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification, proposal 14-F.

Magnesio-arfvedsonite, the CFe3+-dominant analogue of eckermannite, has been found in a sample of “szechenyite” in the mineral collection of the American Museum of Natural History (AMNH H35024). It comes from the northern part of the Jade Mine Tract near Hpakan, Kachin State, Myanmar. Associated minerals are kosmochlor–jadeite solid-solution pyroxene and clinochlore. The ideal formula of magnesio-arfvedsonite is ANaBNa2C(Mg4Fe3+)TSi8O22W(OH)2, and the empirical formula derived from electron microprobe analysis and single-crystal structure refinement for the sample of this work is A(Na0.96K0.04)Σ=1.00B(Na1.57Ca0.40Fe0.022+Mn0.01)Σ=2.00C(Mg4.26Fe0.192+Fe0.413+Al0.11Ti0.034+)Σ=5.00T(Si7.99Al0.01)Σ=8.00O22W[F0.02(OH)1.98]Σ=2.00. The unit-cell dimensions are a = 9.867(1), b = 17.928(2), c = 5.284(1) Å, β = 103.80(2)°, V = 907.7 (2) Å3, Z = 2. Magnesio-arfvedsonite is biaxial (–), with α = 1.624, β = 1.636, γ = 1.637, all ± 0.002 and 2Vobs = 36(1)°, 2Vcalc = 32°. The ten strongest reflections in the X-ray powder pattern [d values (in Å), I, (hkl)] are: 2.708, 100, (151); 3.399, 68, (131); 3.144, 63, (310); 2.526, 60, (202); 8.451, 46, (110); 3.273, 39, (240); 2.167, 37, (261); 2.582, 34, (061); 2.970, 34, (221); 2.326, 33, [(251) (421)].

Byrudite (IMA 2013-045, Raade et al., 2013), with simplified formula (Be,〈)(V3+,Ti)3O6, occurs in emerald-bearing syenitic pegmatites of Permian age at Byrud farm, Eidsvoll, Akershus, South Norway. It has a norbergite-type structure, Pnma, with a = 9.982(1), b = 8.502(1), c = 4.5480(6) Å, V = 385.97(9) Å3, Z = 4. The structure was refined to R1 = 0.045 for 1413 unique reflections. Twinning occurs on {210}. The occupancy of the tetrahedral Be site refined to 0.84(1). The presence of Be was verified by secondary ion mass spectrometry but could not be quantified. Electron-microprobe analyses of the crystal used for structure determination gave the empirical formula (Be0.84〈0.16) (V1.323+Ti1.25Cr0.29Fe0.09Al0.07)Σ3.02O6. There is a strong inverse correlation between V and Cr. The ideal endmember formula is BeV23+TiO6. The mineral is black and opaque with a metallic lustre. Reflectance data in air are reported from 400 to 700 nm. The Commission on Ore Mineralogy required wavelengths are [R1, R2(λ in nm)]:16.6,17.5(470), 16.7,17.9(546), 16.8,18.3(589) and 16.8,18.6(650). The Mohs hardness is ∼7, based on indentation measurements. The mineral is brittle with an uneven fracture; cleavage is not present. D(calc.) = 4.35 g cm–3 for the empirical formula with 0.84 Be a.p.f.u. The strongest reflections of the calculated powder X-ray diffraction pattern are [d in Å (Irel)(hkl)]: 3.721(72)(111), 2.965(100)(121), 2.561(50)(311), 2.464(41)(230), 2.167(24)(231), 1.681(34)(402), 1.671(66)(232), 1.435(23)(630).

Almeidaite (IMA 2013-020), ideally Pb(Mn, Y)Zn2(Ti,Fe3+)18O36(O, OH)2, from Novo Horizonte, Bahia, Brazil, occurs in association with quartz, rutile, anatase, hematite, kaolinite, muscovite, xenotime-(Y) and bastnaesite-(La). Almeidaite forms isolated, black, opaque, sub-metallic, platy crystals flattened on [0001], measuring up to 30 mm 6 30 mm 6 6 mm in size, dominated by the basal pinacoid {0001}, which is bounded by various, mostly steep, rhombohedra and the hexagonal prism {1120}. Most of the crystals are multiply twinned, with non-planar contact surfaces that are approximately parallel to the c axis. The streak is brown. Reflectance values are [(Ro, Re) λ (nm)]: (12.78, 15.39) 470; (12.86, 15.43) 546; (12.91, 15.55) 589; (13.04, 15.75) 650. The empirical formula is (Pb0.59Sr0.12Ca0.04La0.03)Σ0.78(Mn0.54Y0.46)Σ1.00Zn1.43(Ti13.02Fe4.983+)Σ18.00(Fe0.323+Mn0.15)Σ0.47[O37.18(OH)0.82]Σ38.00. It is trigonal, space group R3, with the unit-cell parameters a = 10.4359(2), c = 21.0471(4) Å, V = 1985.10(7) Å3 and Z = 3. The crystal structure was solved (R1 = 0.039) using 2110 unique reflections with I > 3σ(I). Almeidaite is a member of the crichtonite group with Pb dominant in the A site (with 12-fold coordination) and Zn dominant in the T site (with 4-fold coordination). It is a Zn analogue of senaite and a Pb analogue of landauite. The mineral is named after Professor Fernando Flávio Marques de Almeida (1916–2013).

In this work a single crystal of synthetic hercynite, FeAl2O4, was investigated by X-ray diffraction up to 7.5 GPa and at room temperature, in order to determine its pressure–volume equation of state. The unit-cell volume decreases non-linearly with a reduction of 3.4% (i.e. 18.43 Å3). The pressure–volume data were fitted to a third-order Birch-Murnaghan equation of state providing the following coefficients: V0 = 542.58(3)Å3, KT0 = 193.9(1.7) GPa, K' = 6.0(5). These results are consistent with previous investigations of Cr and Al spinels measured with the same experimental approach but the KT0 differs significantly from the experimental determination carried out more than 40 years ago by Wang and Simmons (1972) by the pulse echo overlap method. Our new results were used to redetermine the FeAl2O4(hercynite) = FeO(wüstite) + Al2O3(corundum) equilibrium in P–T space and obtain geobarometric information for Cr-Al spinels found as inclusions in diamond.

Palladosilicide, Pd2Si, is a new mineral (IMA 2014-080) discovered in chromite-rich samples from the Kapalagulu intrusion, western Tanzania (30°03′51′′E 5°53′16′′S and 30°05′37′′E 5°54′26′′S) and from the UG-2 chromitite, Bushveld complex, South Africa. A total of 13 grains of palladosilicide, ranging in size from 0.7 to 39.1 μm (equivalent circle diameters), were found. Synthetic Pd2Si is hexagonal, space group P62m, with a = 6.496(5), c = 3.433(4) Å, V = 125.5(1) Å3, c:a = 0.529 with Z = 3. The strongest lines calculated from the powder pattern (Anderko and Schubert, 1953) are [d in Å (I) (hkl)] 2.3658 100 (111); 2.1263 37 (120); 2.1808 34 (021); 3.240 20 (110); 1.8752 19 (030); 1.7265 12 (002); 1.3403 11 (122); 1.2089 10 (231). The calculated density for three analyses varies from 9.562 to 9.753 g cm–3. Palladosilicide is considered to be equivalent to synthetic Pd2Si based on results from electron backscattered diffraction analyses. Reflectance data in air for the four Commission on Ore Mineralogy wavelengths are [λ nm, R1 (%) R2 (%)] 470 49.6 52.7; 546 51.2 53.8; 589 51.6 53.7; 650 51.7 53.3 and the mineral is bright creamy white against chromite, weakly bireflectant and displays no discernible pleochroism or twinning. It is weakly anisotropic, has weak extinction and rotation tints in shades of blue and olive green. Electron probe microanalyses of palladosilicide yield a simplified formula of Pd2Si.

Crystals of laueite, Mn2+Fe23+(PO4)2(OH)2·8H2O, from the Cornelia mine open cut, Hagendorf Süd, Bavaria, are zoned due to aluminium incorporation at the iron sites, with analysed Al2O3 contents varying up to 11 wt.%. Synchrotron X-ray data were collected on two crystals with different Al contents and the structures refined. The laueite structure contains two independent Fe3+-containing sites; M2 and M3, which alternate in 7 Å corner-connected octahedral chains. The coordination polyhedra are different for the two sites, M2O4(OH)2 and M3O2(OH)2(H2O)2 respectively. The structure refinements show that Al preferentially orders into site M3. Refined site occupancies for M2 and M3 for the two crystals are: for crystal L-1, M2 = 0.70(1) Fe + 0.30(1) Al, M3 = 0.54(1) Fe + 0.46(1) Al and for crystal L-2, M2 = 0.67(1) Fe + 0.33(1) Al, M3 = 0.48(1) Fe + 0.52(1) Al. For crystal L-2, the octahedral chains have dominant Fe in M2, alternating with dominant Al in M3 along the chain, an ordering phenomenon not previously reported for laueite-related minerals.

We report the single-crystal average structure of cyanotrichite, Cu4Al2[SO4](OH)12(H2O)2, from the Maid of Sunshine mine, Arizona, USA. Cyanotrichite crystallizes in space group C2/m, with the unit-cell parameters a = 12.625(3), b = 2.8950(6), c = 10.153(2) Å and β = 92.17(3)o. All non-hydrogen atoms were located and refined to R1 = 0.0394 for all 584 observed reflections [Fo > 4σFo] and 0.0424 for all 622 unique reflections. The cyanotrichite structure consists of a principal building unit of a three-wide [Cu2Al(OH)6] ribbon of edge-sharing Cu and Al polyhedra || b, similar to that found for camerolaite. The ribbons lie in layers || (001) and between these layers, while SO4 tetrahedra and H2O molecules form rods running || b. A hydrogen-bonding scheme is also proposed.

A sample of cyanotrichite from the Cap Garonne mine, Le Pradet, France, showed a 4b superstructure with the following unit cell: space group P2/m, a = 12.611(2) Å, b = 11.584(16) = 4 × 2.896(4) Å, c = 10.190(1) Å and β = 92.29(6)o. The supercell could not be refined in detail, but nevertheless imposes constraints on the local structure in that while the space-group symmetry prevents full order of SO4 and H2O in the 4b supercell, it requires that the sequence of species along any given rod is [-SO4-SO4-(H2O)2-(H2O)2-] rather than [-SO4-(H2O)2-SO4-(H2O)2-].

We have applied mechanical exfoliation for the preparation of ultra-thin samples of the phyllosilicate mineral biotite. We demonstrate that the 'scotch tape' approach, which was made famous as an early method for production of single-atom-thick graphene, can be used for production of sheet-silicate specimens that are sufficiently thin to allow high-resolution transmission electron microscope (HRTEM) imaging to be achieved successfully while also being free from the specimen preparation artefacts that are often caused by ion-beam milling techniques. Exfoliation of the biotite parallel to the (001) planes has produced layers as thin as two structural TOT units thick (∼2 nm). The minimal specimen thickness enabled not only HRTEM imaging but also the application of subsequent exit wavefunction restoration to reveal the pristine biotite lattice. Exit wavefunction restoration recovers the full complex electron wave from a focal series of HRTEM images, removing the effects of coherent lens aberrations. This combination of methods therefore produces images in which the observed features are readily interpreted to obtain atomic resolution structural information.

Tapiaite (IMA2014-024), Ca5Al2(AsO4)4(OH)4·12H2O, is a new mineral from the Jote mine, Tierra Amarilla, Copiapó Province, Atacama, Chile. The mineral is a late-stage, low-temperature, secondary mineral occurring with conichalcite, joteite, mansfieldite, pharmacoalumite, pharmacosiderite and scorodite in narrow seams and vughs in the oxidized upper portion of a hydrothermal sulfide vein hosted by volcanoclastic rocks. Crystals occur as colourless blades, flattened on {101} and elongated and striated along [010], up to ∼0.5 mm long, and exhibiting the forms {101}, {101} and {111}. The blades are commonly intergrown in subparallel bundles and less commonly in sprays. The mineral is transparent and has a white streak and vitreous lustre. The Mohs hardness is estimated to be between 2 and 3, the tenacity is brittle, and the fracture is splintery. It has two perfect cleavages on {101} and {101}. The calculated density based on the empirical formula is 2.681 g cm–3. It is optically biaxial (+) with α = 1.579(1), β = 1.588(1), γ = 1.610(1) (white light), 2Vmeas = 66(2)° and 2Vcalc = 66°. The mineral exhibits no dispersion. The optical orientation is X ≈ [101]; Y = b, Z ≈ [101]. The electron-microprobe analyses (average of five) provided: Na2O 0.09, CaO 24.96, CuO 0.73, Al2O3 10.08, Fe2O3 0.19, As2O5 40.98, Sb2O5 0.09, H2 O 23.46 (structure), total 100.58 wt.%. In terms of the structure, the empirical formula (based on 32 O a.p.f.u.) is (Ca4.83Cu0.102+Na0.03)Σ4.96(Al2.14Fe0.033+)Σ2.17[(As3.875+Sb0.015+)Σ3.88O16][(OH)3.76(H2O)0.24]Σ4(H2O)10·2H2O. The mineral is easily soluble in RT dilute HCl. Tapiaite is monoclinic, P21/n, with unit-cell parameters a = 16.016(1), b = 5.7781(3), c = 16.341(1) Å, β = 116.704(8)°, V = 1350.9(2) Å3 and Z = 2. The eight strongest lines in the powder X-ray diffraction pattern are [dobs Å(I)(hkl)]: 13.91(100)(101), 7.23(17)(200,002), 5.39(22)(110,011), 4.64(33)(112,211,303), 3.952(42)(113,311,213), 3.290(35)(214,412,114,411), 2.823(39)(303,315) and 2.753(15)(513,115,121,511). The structure of tapiaite (R1 = 5.37% for 1733 Fo > 4σF) contains Al(AsO4)(OH)2 chains of octahedra and tetrahedra that are topologically identical to the chain in the structure of linarite. CaO8 polyhedra condense to the chains, forming columns, which are decorated with additional peripheral AsO4 tetrahedra. The CaO8 polyhedra in adjacent columns link to one another by corner-sharing to form thick layers parallel to {101} and the peripheral AsO4 tetrahedra link to CaO6 octahedra in the interlayer region, resulting in a framework structure.

Katophorite has the ideal formula ANaB(NaCa)C(Mg4Al)T(Si7Al)O22W(OH)2 (Hawthorne et al., 2012). No published analyses of amphiboles fall in the katophorite compositional field, except that of Harlow and Olds (1987) for an amphibole from near Hpakan in the Jade Mine Tract, Myanmar. This amphibole was approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (vote 2013-140) as katophorite, and is reported here. Holotype katophorite is monoclinic, space group C2/m, a = 9.8573(8), b = 17.9617(15), c = 5.2833(4) Å, β = 104.707(2)°, V = 904.78(13) Å3, Z = 2. The calculated density is 3.091 g cm–3. In plane-polarized light, katophorite is pleochroic, X = pale blue (medium), Y = light blue-green (strongest), Z = colourless; X ∧ a = 30.6° (β obtuse), Y || b, Z ∧ c = 15.8 (β acute). It is biaxial negative, α = 1.638, β = 1.642, γ = 1.644, all ± 0.002; 2Vobs = 73(1)°, 2Vcalc = 70°. The eight strongest lines in the powder X-ray diffraction pattern are [d in Å (I)(hkl)]: 2.700 (100)(151), 3.129 (69)(310), 2.536 (65)(202), 3.378 (61)(131), 8.421 (55)(110), 2.583 (46)(061), 2.942 (43)(221) and 2.334 (41)(351). Electron-microprobe analysis of the refined crystal gave SiO251.74, Al2O37.38, TiO2 0.14, FeO 1.55, Fe2O3 2.82, MgO 18.09, CaO 8.17, Na2O 6.02, K2O 0.24, F 0.06, H2Ocalc. 1.80, Li2Ocalc. 0.09, sum 100.55 wt.% (Li2O and H2O based on the results of single-crystal structure refinement). The formula unit, calculated on the basis of 24 (O,OH,F) with (OH + F + O) = 2 is: A(Na0.85K0.04)Σ=0.89B(Ca1.22Na0.78)Σ=2.00C(Mg3.76Al0.43Fe0.303+Cr0.273+Fe0.182+Li0.05Ti0.014+)Σ=5.00T(Si7.21Al0.79)Σ=8.00O22W[(OH)1.67O0.30F0.03)]Σ=2.00.

A new mineral chrysothallite K6Cu6Tl3+Cl17(OH)4·H2O was found in two active fumaroles, Glavnaya Tenoritovaya and Pyatno, at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. Chrysothallite seems to be a product of the interactions involving high-temperature sublimate minerals, fumarolic gas and atmospheric water vapour at temperatures not higher than 150ºC. It is associated with belloite, avdoninite, chlorothionite, sanguite, eriochalcite, mitscherlichite, sylvite, carnallite and kainite at Glavnaya Tenoritovaya and with belloite, avdoninite, chlorothionite, eriochalcite, atacamite, halite, kröhnkite, natrochalcite, gypsum and antlerite at Pyatno. The mineral forms equant-to-thick tabular crystals up to 0.05 mm, typically combined in clusters or crusts up to 1 mm across. Crystal forms are: {001}, {100}, {110}, {101} and {102}. Chrysothallite is transparent, bright golden-yellow to light yellow in finely crystalline aggregates. The lustre is vitreous. The mineral is brittle. Cleavage was not observed, the fracture is uneven. Dmeas = 2.95(2), Dcalc = 2.97 g cm–3. Chrysothallite is optically uniaxial (+), ω = 1.720(5), ε = 1.732(5). The Raman spectrum is given. The chemical composition (wt.%, electron-microprobe data, H2O calculated based on the crystal structure data) is: K 15.92, Cu 24.56, Zn 1.38, Tl 13.28, Cl 40.32, H2O(calc.) 3.49, total 98.95. The empirical formula, calculated on the basis of 17 Cl + 5 O a.p.f.u., is: K6.09(Cu5.78Zn0.32)Σ6.10Tl0.97Cl17[(OH)3.80O0.20]·H2O. Chrysothallite is tetragonal, I4/mmm, a = 11.3689(7), c = 26.207(2) Å, V = 3387.3(4) Å3, Z = 4. The strongest reflections of the powder X-ray pattern [d, Å (I)(hkl)] are: 13.20(44)(002); 6.88(100)(112); 5.16(30)(202, 114); 4.027(25)(220); 3.471(28)(206), 3.153(30)(314), 3.075(47)(305), 2.771(38)(316). The crystal structure (solved from single-crystal X-ray diffraction data, R = 0.0898) is unique. Its basic structural unit is a (001) layer of edge-sharing distorted CuCl4(OH)2 octahedra. Two Tl3+ cations occupy the centre of isolated TlCl6 and TlCl4(H2O)2 octahedra connected to each other and to the Cu polyhedral layers via KCl6 and KCl9 polyhedra. The name reflects the bright golden-yellow colour of the mineral (from the Greek χρυσος, gold) and the presence of thallium. Chrysothallite is the second known mineral with species-defining trivalent thallium.

A monoclinic form of Fe3S4, a polymorph of cubic greigite, occurs as precipitates in a sample of pyrrhotite collected from the Sudbury ore deposit. The nano-crystal precipitates are in a topotaxial relationship with the host pyrrhotite-4C (Fe7S8). The precipitate and the host pyrrhotite have a coherent (001) interface. Half of the octahedral layers in the crystal structure are fully occupied by Fe, while the other half of the octahedral layers are occupied by Fe atoms and vacancies in an ordered manner along the a axis. The crystal structure of the Fe3S4 nano-precipitates has monoclinic symmetry with a space group of I2/m. Its c dimension is 6% smaller than that of the host pyrrhotite due to the large number of vacancies in the structure. Fractional coordinates for S and Fe atoms within the unit cell are determined from Z-contrast images and density functional theory (DFT). The calculated results match the measured values very well. It is proposed that the monoclinic Fe3S4 nano-precipitates formed through ordering of vacancies in pyrrhotite with a low Fe/S ratio (i.e. <0.875) at low temperature.

Moraskoite, a new natural phosphate of composition Na2Mg(PO4)F, has been found in the Morasko IAB-MG iron meteorite. The new phosphate occurs in a graphite-troilite inclusion enclosed in a kamacite-taenite matrix. Associated minerals in the inclusions are chlorapatite, buchwaldite, brianite, merrillite, a new phosphate phase of composition Na4MgCa3(PO4)4, chromite, enstatite (bronzite), kosmochlor, kosmochlor–augite, olivine, albite, orthoclase, quartz, cohenite, schreibersite, nickelphosphide, altaite, pyrrhotite, sphalerite, daubreelite, djerfischerite, whitlockite and native Cu. The inclusions are rimmed by a schreibersite-cohenite halo. Moraskoite forms aggregates up to 1.5 mm in size, with individual grains 20–300 μm across. It is colourless and transparent, with a white streak and vitreous lustre; fluorescence is weak blue in ultraviolet radiation (254 and 360 nm); hardness is 4–5; it has irregular, conchoidal fracture and cleavage is rarely observed. Calculated density (using the empirical formula) is 2.925 g cm–3. The moraskoite structure (Pbcn, a = 5.2117(10), b = 13.711(3), c = 11.665(2) Å, V = 833.6(3) Å3 and Z = 8) is similar to that of its synthetic analogue. The strongest diffraction lines of the moraskoite powder diffraction pattern are as follows (dhkl, I): 3.909(75), 3.382(52), 2.955(90), 2.606(100), 2.571(96), 2.545(68), 1.691 (67). In the Raman spectrum, the following characteristic bands are distinguished (cm–1, strong bands bold): 1114, 1027, 962, 589, 438, 336, 308, 279, 262, 244, 193, 184, 147 and 131. The Raman data prove the absence of H2O and CO2. Moraskoite is interpreted as being a primary phosphate, which crystallized together with graphite, troilite and other accessories inside the nodule.

Carbonated strontium fluor-, hydroxyl- and chlorapatites (carbonated Sr10(PO4)6X2 = CSrApX, where X= OH, Cl and F) were synthesized in aqueous solution. The substitution mode of carbonate was determined from infrared (IR) stretching frequencies for carbonate and from the variation in unit-cell axial lengths as a function of carbonate content. The a-axis lengths of CSrApF and CSrApCl decrease, whereas the a-axis length of CSrApOH increases slightly with increasing carbonate substitution. The carbonate IR stretching region from ∼1390 to 1590 cm–1 contains two doublets for both CSrApOH and CSrApCl, indicating the presence of both A- and B-type carbonate. The carbonate spectral region for CSrApF is reminiscent of that for CCaApF, which contains one doublet for B-type carbonate with a small shoulder attributable to A-type carbonate. Activity-based Ksp values (assuming B-type substitution) were determined for all three series of carbonated Sr apatites and show that the solubilities of CSrApOH and CSrApCl increase at higher carbonate values, whereas those of CSrApF stay constant. The Ksp values for uncarbonated SrApOH, SrApCl and SrApF were determined by extrapolation to zero percent carbonate (10–120, 10–112 and 10–113 for SrApOH, SrApCl and SrApF, respectively).

Imayoshiite, Ca3Al(CO3)[B(OH)4](OH)6·12H2O, occurs in cavities in the altered gabbro xenolith in the sepentinized dunite exposed at Suisho-dani, Ise City, Mie Prefecture, Japan. Imayoshiite is colourless and transparent with a vitreous lustre and its aggregates are white with a silky lustre. Imayoshiite has a white streak. Its Mohs hardness is 2–3. It is brittle, the cleavage is distinct on {100} and the fracture is uneven. The mineral is uniaxial (–) with the indices of refraction ω = 1.497(2) and ε = 1.470(2) in white light. Imayoshiite is hexagonal, P63, a = 11.0264(11), c = 10.6052(16) Å by powder diffraction and a = 11.04592(2), c = 10.61502(19) Å by single-crystal diffraction. The structural refinement converged to R1 = 2.35%. Imayoshiite is the first member of the ettringite group with both CO3 and B(OH)4 anions.

The crystal structure of the spinel-related, Sb mineral tegengrenite from the Filipstad district, Värmland, Sweden, has been solved in the space group R3 [a = 16.0285(9), c = 14.8144(8) Å, V = 3296.1(3) Å3, Z = 42] and refined up to R = 0.0484 for 3589 reflections with Fo > 4σ(Fo). Tegengrenite exhibits a rhombohedrally distorted spinel-type structure with cations occupying 1/8 of the tetrahedral (T) and 1/2 of the octahedral (M) interstices of a nearly regular cubic close-packing of oxygen atoms. Due to the cation ordering, which leads to a complex superstructure with a unit-cell volume of 21/4 that of a common spinel, the M and T sites of the spinel-type structure split into ten and six independent sites, respectively. Chemical composition determined by electron microprobe led to the empirical formula Mg1.26Mn0.852+Zn0.04Mn0.193+Al0.01Si0.12Ti0.03Sb0.505+O4, on the assumption that no vacancies occur in the mineral (Σcat = 3.00 and Σcharge = 8.00 per formula unit). Crystal-chemical considerations indicate that octahedra are occupied mainly by Mg, Mn3+ and Sb5+ (+Al, + Ti), whereas tetrahedra are filled mainly by Mn2+ and Mg (+Zn) with Si ordered in a specific site. However, the structure refinement shows a low site-scattering factor for one octahedral site, implying substantial vacancies and a larger overall mean Mn valence than stated above. Long mean distances also suggest some Mn2+ on octahedral sites. Together, these observations necessitate the presence of substantial Mn3+ on tetrahedral sites.

Calcium silicate hydrate (C-S-H) alteration was studied with flow-through experiments at 25°C and pH 9.2. Three materials with apparent Ca/Si ratios (C/S ratios) of 1.47, 1.38 and 0.86 were investigated. Physical (thermogravimetric analyses/differential thermal analysis), mineralogical (X-ray diffraction) and chemical (electron probe microanalysis, transmission electron microscopy/energy dispersive X-ray spectrometry) analyses were performed to characterize the reacting minerals. Initial stoichiometric C/S ratios were 1.22, 1.22 and 0.85, respectively. The excess of Ca is attributed mainly to the presence of calcium hydroxide intimately mixed in with C-S-H particles.

The C-S-H chemical compositions were monitored during flow-through experiments in order to determine the mineral stoichiometry needed for reaction kinetics. Under our experimental conditions the stoichiometric C/S ratios decreased continuously with time. A close to stoichiometric dissolution was observed after 2 days of experiments. Using an integrated approach, the kinetics was found to be a function of the C/S.

A decrease in layer-to-layer distance in the early stage of the alteration process is interpreted as interlayer Ca/Na exchange (Na being part of the pH buffering solution). A second dissolution step, marked by a close to stoichiometric release of Ca and Si, undoubtedly results from layer dissolution. The structural similarity of C-S-H and tobermorite was confirmed.