The new mineral popovite, Cu5O2(AsO4)2, was found in the 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 ericlaxmanite, kozyrevskite, urusovite, lammerite, lammerite-β, johillerite, bradaczekite, tenorite, hematite, aphthitalite, anhydrite, langbeinite, calciolangbeinite, As-bearing orthoclase, etc. Popovite occurs as prismatic or tabular crystals and as grains up to 0.2 mm in size forming clusters up to 1.5 mm in size and as crusts on basalt scoria or on aphthitalite incrustations. Popovite is transparent with a vitreous to greasy lustre. Its colour is olive green to dark olive-green, but fine-grained varieties are light yellow-green. The mineral is brittle, with Mohs' hardness ∼3½. Cleavage was not observed and the fracture is uneven. Dcalc is 5.30 g cm–3. Popovite is optically biaxial (+), α = 1.84(1), β ≈ 1.86, γ = 1.96(1), 2Vmeas = 50(20)°. The Raman spectrum is given. Chemical data (wt.%, electron-microprobe) are CuO 63.28, ZnO 0.56, V2O50.12, As2O5 35.80, SO3 0.27, total 100.03. The empirical formula, based on 10 O a.p.f.u., is (Cu4.99Zn0.04)Σ5.03(As1.95S0.02V0.01)Σ1.98O10. Popovite is triclinic, P1̄, a = 5.1450(3), b = 6.2557(3), c = 6.2766(4) Å, α = 100.064(5), β = 96.351(5), γ = 95.100(5)°, V = 196.47(1) Å3 and Z = 1. The strongest reflections in the powder X-ray diffraction pattern [d, Å (I)(hkl)] are 3.715(36)(110, 101), 3.465(43)(11̄1), 2.968(90)(01̄2), 2.927(100)(111), 2.782(31)(1̄02), 2.768(67)(1̄20), 2.513(55)(1̄2̄1) and 2.462(67)(2̄01). Popovite has a novel structure type. Its crystal structure, solved from single-crystal X-ray diffraction data (R = 0.0459), is based on (010) layers forming an interrupted framework. The layer consists of Cu(1)O6 octahedra with very strong Jahn-Teller distortion and Cu(2)O5 and Cu(3)O5 polyhedra. The linkage between the layers is reinforced by isolated AsO4 tetrahedra. Popovite is named in honour of the Russian mineralogists Vladimir Anatol'evich Popov (b. 1941) and Valentina Ivanovna Popova (b. 1941), a husband and wife research team working in the Institute of Mineralogy of the Urals Branch of the Russian Academy of Sciences, Miass, Russia.

Microcrystals of platinum-group element (PGE)-bearing cobaltite occur in the Gulcari A deposit of vanadiferous titanomagnetite in the lower zone of the Rio Jacaré mafic-ultramafic layered intrusion, Brazil. Aggregates of cobaltite and sperrylite are cluster-like and developed generally along the boundary of Fe-Ti oxide grains with deuteric silicates. Our observations of cryptic zoning, compositional variability and interelement correlations are based on 37 analytical points (wavelength-dispersion spectrometry mode) of cobaltite, and indicate that Ir and Rh behave uniformly with Ni and antipathetically with Co which, in turn, correlates directly with S content. Iridium, Rh and Ni apparently substitute for Co in the As-enriched grain core, and the substitution mechanism invokes solid solution with a cattierite-type molecule: (Ni + Ir + Rh) + (AsS) = Co + (S2). The PGE-bearing cobaltite probably crystallized as a primary phase at 500 to 300°C, from microvolumes of a late fluid phase. The observed enrichment in S and decrease in the As:S ratio at the cobaltite grain margins is a reflection of the increase in sulfur fugacity (fS2) with decrease in temperature of crystallization.

The new pyroxenoid barrydawsonite-(Y) occurs at the Merlot Claim, North Red Wine Pluton, Labrador, Canada (62°32'38.54'' W; 54°08'1.37'' N). The host rock is a metamorphosed eudialyte syenite consisting of eudialyte, potassic arfvedsonite, jadeitic aegirine, nepheline, albite and potassium feldspar with accessory Y-bearing pectolite, britholite and steenstrupine. Barrydawsonite-(Y) crystals commonly have discrete thin rims of Y-bearing pectolite. The average empirical formula (based on nine anions p.f.u.) is Na1.54Ca0.74Mn0.15Fe0.07Y0.38Nd0.01Sm0.01Gd0.02Tb0.01Dy0.04Ho0.01Er0.02Yb0.01Si3.00O9H. The simplified formula is Na1.5Y0.5CaSi3O9H. Barrydawsonite-(Y) is related to pectolite by the substitution ½[NaM3+Ca–2] (M3+ = Y,REE), and is exceptional in being the only member of the pectolite group that has the structure of the monoclinic M2abc polytype. The crystal structure has been determined in monoclinic space group P21/a: a = 15.5026(2), b = 7.0233(1), c = 6.9769(1) Å, β = 95.149(1)°, V = 756.58(2) Å3(Z = 4). Final agreement indices are R1 = 0.038, wR2 = 0.068, Goof = 1.136. The asymmetric unit of barrydawsonite-(Y) has three metal sites: M(1) = Ca, M(2) = Na0.5(Y,REE)0.5, M(3) = Na. M(1) and M(2) are octahedrally-coordinated sites, whereas M(3) is [8]-coordinated as in pectolite and serandite. The structural formula for the empirical composition is M(3)Na1.00M(2)(Na0.50Y0.38REE0.13)Σ=1.01M(1)(Na0.04Ca0.74Mn0.152+Fe0.072+)Σ=1.00Si3O9H. There is excellent agreement between the refined site-scattering values and those calculated based upon the structural formula.

Barrydawsonite-(Y) is biaxial (+) with α = 1.612(1), β = 1.617(1), γ = 1.630(1) (white light) and 2V = 63(1)°. The five strongest peaks in the X-ray powder diffraction pattern are [dobs (Å), Iobs%, (hkl)]: [2.905, 100, (023)], [3.094, 30, (210,211,121,202)], [1.7613, 29, (127,323,040)], [3.272, 27, (202,104)], [1.7016, 27, (140,227,325)].

'Clinobarylite', BaBe2Si2O7, was defined as a monoclinic dimorph of orthorhombic barylite. Subsequently, its crystal structure was also proved to be orthorhombic, differing from barylite in terms of the space group symmetry, Pmn21 instead of Pmnb, and in unit-cell dimensions. Through the order-disorder (OD) theory, the polytypic relationships between 'clinobarylite' and barylite are described. 'Clinobarylite' corresponds to the MDO1 polytype, with unit-cell parameters a = 11.650, b = 4.922, c = 4.674 Å, space group Pmn21; barylite corresponds to the MDO2 polytype, with a = 11.67, b = 9.82, c = 4.69 Å, space group Pmnb. The re-examination of the holotype specimen of 'clinobarylite' confirmed its orthorhombic symmetry. Its crystal structure has been refined starting from the atomic coordinates calculated for the MDO1 polytype and the refinement converged to R1 = 0.0144 for 929 observed reflections [Fo > 4σFo]. Owing to their polytypic relationships, 'clinobarylite' and barylite should be conveniently indicated as barylite-1O and barylite-2O, respectively; the name 'clinobarylite' should be discontinued. This new nomenclature of the barylite polytypes has been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA 13-E).

Opalinus clay has a high sealing capacity and is therefore considered as a viable candidate for hosting high-level radioactive waste. Assessment of the long-term containment function of clays requires understanding and modelling of mass transport through evolving pore systems. Development of pore network models for diffusion, which can be coupled to models for deformation and micro-cracking, is reported. Effects of clay texture and solid phase constitution are calculated and analysed. The results are in the range of, but slightly over-predicting, experimentally measured coefficients of diffusion in different clay directions. Further model improvements require better knowledge of micro-pore tortuosity, which awaits higher resolution experimental techniques.

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.

Eckerite, ideally Ag2CuAsS3, is a new mineral from the Lengenbach quarry in the Binn Valley, Valais, Switzerland. It occurs as very rare euhedral crystals up to 300 μm across associated with realgar, sinnerite, hatchite, trechmannite and yellow, fibrous smithite. In thick section eckerite is opaque with a metallic lustre and shows a dark orange-red streak. It is brittle; the Vickers hardness (VHN25) is 70 kg/mm2 (range: 64–78) (Mohs hardness of ∼2½–3). In reflected light, eckerite is moderately bireflectant and weakly pleochroic from light grey to a slightly bluish grey. Internal reflections are absent. Under crossed nicols, it is weakly anisotropic with greyish to light blue rotation tints. Reflectance percentages for Rmin and Rmax are 27.6, 31.7 (471.1 nm), 22.8, 26.1 (548.3 nm), 21.5, 24.5 (586.6 nm) and 19.4, 22.3 (652.3 nm), respectively.

Eckerite is monoclinic, space group C2/c, with a = 11.8643(3), b = 6.2338(1), c = 16.6785(4) Å, β = 110.842(3)°, V = 1152.81(5) Å3, Z = 8. The crystal structure [R1 = 0.0769 for 1606 reflections with Fo > 4σ(Fo)] is topologically identical to that of xanthoconite and pyrostilpnite. In the structure, AsS3 pyramids are joined by AgS3 triangles to form double sheets parallel to (001); the sheets are linked by Cu(Ag) atoms in a quasi-tetrahedral coordination. Among the three metals sites, Ag2 is dominated by Cu. The mean metal–S distances reflect well the Ag ↔ Cu substitution occurring at this site.

The eight strongest powder X-ray diffraction lines [d in Å (I/I0) (hkl)] are: 3.336 (70) (312); 2.941 (100) (314,114); 2.776 (80) (400,206); 2.677 (40) (312); 2.134 (50) (421); 2.084 (40) (208,206); 2.076 (40) (420); 1.738 (40) (228,226). A mean of five electron microprobe analyses gave Ag 52.08(16), Cu 11.18(9), Pb 0.04(1), Sb 0.29(3), As 15.28(11), S 20.73(13), total 99.60 wt.%, corresponding, on the basis of a total of 7 atoms per formula unit, to Ag2.24Cu0.82As0.94Sb0.01S2.99. The new mineral has been approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (2014–063) and named for Markus Ecker, a well known mineral expert on the Lengenbach minerals for more than 25 years.

Minjiangite, ideally BaBe2(PO4)2, is a new mineral species which has been found in the Nanping No. 31 pegmatite, Fujian Province, southeastern China. It occurs in the fractures of montebrasite from pegmatite zone IV, and is associated with quartz, muscovite, hydroxylapatite and palermoite. Minjiangite forms subhedral to euhedral white crystals from 5 to 200 μm long, transparent to translucent, with a vitreous lustre. The estimated Mohs hardness is ∼6, the tenacity is brittle and no cleavage was observed. The calculated density is 3.49 g/cm3. Optically, minjiangite is uniaxial (+), with ω = 1.587(3), ε = 1.602(2) (λ = 589 nm). Electron-microprobe analyses (average of 8) give P2O5 40.16, BaO 43.01, BeO 14.06 (measured by Secondary Ion Mass Spectrometry), SiO2 0.17, CaO 0.17, SrO 0.08, FeO 0.03, MgO 0.01, TiO2 0.07, K2O 0.05, Na2O 0.11, total 97.92 wt.%. The empirical formula, calculated on the basis of 8 O a.p.f.u., is (Ba0.99Ca0.01Na0.01)Σ1.01Be1.98(P1.99Si0.01)Σ2.00O8. The powder X-ray diffraction (XRD) pattern of minjiangite perfectly fits that of synthetic BaBe2(PO4)2; the strongest eight lines of the powder XRD pattern of the natural phosphate [d in Å (I)(hkl)] are: 3.763(100)(101); 2.836(81.3)(102); 2.515(32.3)(110); 2.178(25.6)(200); 2.1620(19)(103); 2.090(63.9)(201); 1.770(16.2)(113); 1.507(25.4)(212). Unit-cell parameters, refined from the powder XRD pattern of natural minjiangite, are a = 5.030(8), c = 7.467 (2) Å, V = 163.96(3) Å3. These unit-cell parameters confirm that minjiangite is the natural analogue of synthetic BaBe2(PO4)2(P6/mmm, a = 5.029(1), c = 7.466 (1) Å, V = 163.52(1) Å3, Z = 1); its crystal structure is topologically similar to that of dmisteinbergite, CaAl2Si2O8, a hexagonal polymorph of anorthite. The formation of minjiangite is related to the hydrothermal alteration of montebrasite by late Ba- and Be-rich fluids.

The present work analyses the thermal behaviour of alum-(K), KAl(SO4)2·12H2O, by in situ laboratory high-temperature powder X-ray diffraction data from 303 K to melting, which starts at 355 K and is completed, due to kinetics, at 359 K. The calculated a0 linear thermal expansion coefficient is of 14.68(11) × 10–6 K–1 within the investigated thermal range. The k disorder parameter, describing the extension of the orientational disorder of the sulfate group, has been found to decrease from ∼0.70 to ∼0.65 just before melting. It has been demonstrated that the occurrence of the disorder implies the coexistence of K+ ions in both six- and seven-fold coordination. This is necessary for assigning a reasonable bond-valence sum of 0.81 valence units (vu) to the 'average' K+ ion a instead of 0.66 vu, which is obtained in the case of six-fold coordination alone. We can describe the temperature dependence of k from 93–355 K by means of the empirical equation k = 0.798(12) + 2.5(11) × 10–4 T – 1.9(2) × 10–6T2, which includes reference low-temperature data. Bond-valence analysis has shown that, on cooling, an increase of the k disorder parameter and shortening of the K–O2 bond distance act together to maintain constancy in the bond-valence sum at the K site, stabilizing the structure. Therefore, the need for keeping the 'average' K+ ion at a reasonable bond-valence sum appears to be the driving force for the ordering process involving the sulfate group.

The incorporation of pertechnetate (TcO4–) into feldspathoids produced by alkaline alteration of aluminosilicate clays may offer a potential treatment route for 99Tc-containing groundwater and liquors. Kaolinite was aged in NaOH to determine the effect of base concentration, temperature, and solution composition on mineral transformation and pertechnetate uptake. In all reactions, increased temperature and NaOH concentration increased the rate of kaolinite transformation to feldspathoid phases. In reactions containing only NaOH, sodalite was the dominant alteration product; however, small amounts (6–15%) of cancrinite also formed. In experiments containing NaOH/Cl and NaOH/NO3 mixtures, sodalite and nitrate cancrinite were crystallized (at 70°C), with no reaction intermediates. The addition of SO42– crystallized sulfatic sodalite at 40 and 50°C, but at higher temperatures (60 and 70°C) sulfatic sodalite transforms to vishnevite (sulfatic cancrinite). In experiments where a pertechnetate tracer was added (at ∼1.5 μmol l–1), only 3–5% of the 99Tc was incorporated into the feldspathoid phases. This suggests that the larger pertechnetate anion was unable to compete as favourably for the internal vacancies with the smaller OH–, NO3–, SO42– or Cl– anions in solution, making this method likely to be unsuitable for groundwater treatment.

The new minerals bobcookite (IMA 2014-030), NaAl(UO2)2(SO4)4·18H2O and wetherillite (IMA 2014-044), Na2Mg(UO2)2(SO4)4·18H2O, were found in the Blue Lizard mine, San Juan County, Utah, USA, where they occur together as secondary alteration phases in association with boyleite, chalcanthite, dietrichite, gypsum, hexahydrite, johannite, pickeringite and rozenite.

Bobcookite descriptive details: lime green to greenish-yellow massive veins and columnar crystals; transparent; vitreous lustre; bright greenish-white fluorescence; pale greenish yellow streak; hardness (Mohs) 2½; brittle; conchoidal fracture; no cleavage; moderately hygroscopic; easily soluble in cold H2O; densitycalc = 2.669 g cm–3. Optically, biaxial (–), α = 1.501(1), β = 1.523(1), γ = 1.536(1) (white light); 2Vmeas. = 78(1)°; 2Vcalc. = 74°; dispersion r < v, moderate. Pleochroism: X colourless, Y very pale yellow-green, Z pale yellow-green; X < Y < Z. EDS analyses yielded the empirical formula Na0.97Al1.09(U1.02O2)2(S0.98O4)4(H2O)18. Bobcookite is triclinic, P1, a = 7.7912(2), b = 10.5491(3), c = 11.2451(8) Å , α = 68.961(5), β = 70.909(5), γ = 87.139(6)°, V = 812.79(8) Å3 and Z = 1. The structure (R1 = 1.65% for 3580 Fo > 4σF) contains [(UO2)(SO4)2(H2O)] chains linked by NaO4(H2O)2 octahedra to form layers. Hydrogen bonds to insular Al(H2O)6 octahedra and isolated H2O groups hold the structure together. The mineral is named for Dr Robert (Bob) B. Cook of Auburn University, Alabama, USA.

Wetherillite descriptive details: pale greenish-yellow blades; transparent; vitreous lustre; white streak; hardness (Mohs) 2; brittle; two cleavages, {101} perfect and {010} fair; conchoidal or curved fracture; easily soluble in cold H2O; densitycalc = 2.626 g cm–3. Optically, biaxial (+), α = 1.498(1), β = 1.508(1), γ = 1.519(1) (white light); 2Vmeas. = 88(1)°, 2Vcalc. = 87.9°; dispersion is r < v, distinct; optical orientation: Z = b, X ∧ a = 54° in obtuse β; pleochroism: X colourless, Y pale yellow-green, Z pale yellow-green; X < Y ≈ Z. EDS analyses yielded the empirical formula Na1.98(Mg0.58Zn0.24Cu0.11Fe0.092+)Σ1.02(U1.04O2)2(S0.98O4)4(H2O)18. Wetherillite is monoclinic, P21/c, a = 20.367(1), b = 6.8329(1), c = 12.903(3) Å, β = 107.879(10)°, V = 1709.0(5) Å3 and Z = 2. The structure (R1 = 1.39% for 3625 Fo > 4σF) contains [(UO2)(SO4)2(H2O)] sheets parallel to {100}. Edge-sharing chains of Na(H2O)5O polyhedra link adjacent uranyl sulfate sheets forming a weakly bonded three-layer sandwich. The sandwich layers are linked to one another by hydrogen bonds through insular Mg(H2O)6 octahedra and isolated H2O groups. The mineral is named for John Wetherill (1866–1944) and George W. Wetherill (1925–2006).

Yeomanite, Pb2O(OH)Cl, is a new Pb-oxychloride found in the manganese pod mineral assemblage at Merehead (Torr Works) Quarry, near Cranmore, Somerset, England. Yeomanite is named in joint recognition of Mrs Angela Yeoman (1931–) and her company, Foster Yeoman, who operated Merehead Quarry for aggregate until 2006. The mineral is normally white, occasionally grey, with a white streak and a vitreous to transparent lustre. Invariably intimately associated with mendipite, yeomanite appears to be formed of small, twisted, rope-like fibres growing from the end of columnar mendipite masses, forming loose mats and strands resembling asbestos. Individual fibres are generally <8 mm long, but exceptionally may reach up to 15 mm. There is a perfect cleavage parallel to the long axis of the fibres but this is masked by the fibrous nature, especially as individual fibres break easily. The Dcalc for the ideal formula is 7.303 g/cm3. The mean RI in air at 589 nm is 2.27. The eight strongest reflections in the powder X-ray diffraction pattern [(d in Å) (Intensity) (hkl)] are: 2.880(100)(113); 2.802(78)(006); 3.293(61)(200); 3.770(32)(011); 2.166(22)(206); 1.662(19)(119); 2.050(18)(303); 3.054(17)(105) Yeomanite is orthorhombic, Pnma, a = 6.585(10), b = 3.855(6), c = 17.26(1) Å, V = 438(1) Å3, Z = 4. Yeomanite is a new example of the growing family of lead oxychloride minerals that have a structure based upon oxocentred OPb4 tetrahedra, which, in this mineral, jointly with OHPb3 triangles, form [O(OH)Pb2]+ chains similar to those observed in synthetic Pb2O(OH)I. Yeomanite is structurally related to sidpietersite, penfieldite and laurionite.

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.

Kerimasite {Ca3}[Zr2](SiFe23+)O12, a rare member of the garnet supergroup, has been identified in association with andradite–grossular and their hydrated analogues, monticellite, perovskite, clintonite, anhydrite, hydroxylellestadite–fluorellestadite, spinel, magnetite, brucite, valeriite and other minerals from a Ca-Mg skarn in the exocontact of a granodiorite porphyry intrusion in Vysoká-Zlatno Cu-Au skarn-porphyry deposit, the Štiavnica stratovolcano, Central Slovakia. Kerimasite forms euhedral-to-anhedral crystals, 2 to 100 μm across with 0.73–1.62 atoms per formula unit (a.p.f.u.) Zr (16.2–33.6 wt.% ZrO2), 0.34–0.66 a.p.f.u. Ti (4.6–9.3 wt.% TiO2), 0.01 to 0.05 a.p.f.u. Hf (0.4–1.7 wt.% HfO2: the largest Hf content reported in kerimasite), and small amounts of Sn, Sc and Nb (≤0.02 a.p.f.u.). Tetrahedral Si (0.99–1.67 a.p.f.u.; 9.8–18.1 wt.% SiO2) is balanced by 0.85–1.26 a.p.f.u. Fe3+ and by 0.46–0.76 a.p.f.u. Al. The crystals commonly show regular, oscillatory concentric zoning or irregular patchy internal textures due to Zr, Ti, Fe, Al and Si variations during growth or partial alteration and dissolution-reprecipitation. The main substitutions in kerimasite are Y(Fe,Sc)3+ + ZSi4+ = Y(Zr,Ti,Hf,Sn)4+ + Z(Fe,Al)3+ and Ti4+ = Zr4+. Associated andradite locally contains irregular Ti- and Zr-rich zones with ≤11 wt.% TiO2 and ≤4.4 wt.% ZrO2. In comparison with common Ca-rich garnets, the micro-Raman spectrum of kerimasite shows that many bands shift towards much lower wavenumbers, either due to Fe3+ substitution on the Z site or to the strong influence of neighbouring octahedrally-coordinated Zr4+ on internal vibrations of tetrahedra that share oxygens. The formation of kerimasite, monticellite, perovskite and other phases indicate a relatively Ca-rich and Si, Al-poor environment, analogous to other known occurrences of Ca-Zr garnets (Ca-rich skarns and xenoliths, carbonatites). Kerimasite and associated skarn minerals originated during contact-thermal metamorphism of Upper Triassic marl slates with limestone, dolomite, anhydrite and gypsum by Miocene granodiorite porphyry at T ≈ 700°C and P ≈ 50–70 MPa.

DBE TECHNOLOGY, BGR and GRS are developing a methodology to demonstrate the safety of a repository for high-level waste and spent fuel (HLW/SF) in clays according to the requirements of the German regulating body. In particular, these requirements prescribe that the barrier effect of host rocks must not be compromised by a thermal impact resulting from HLW/SF emplacement. To substantiate and quantify this requirement, we carried out a literature survey of research on thermally-induced changes on clay properties. Effects thus compiled can be divided into thermo-hydro-mechanical and chemical-biological-mineralogical effects and were analysed with regard to their relevance to the integrity of clay host rocks. This analysis identified one effect of major influence within each group: thermal expansion and compaction as well as results of microbial activities. Importantly, it further revealed that a moderate temperature increase above 100°C cannot be expected to compromise the integrity of the geological barrier according to the current knowledge state. Evidence is presented in this paper that temperature increases up to 150°C can actually contribute to an improved performance of a radioactive waste repository by increasing the consolidation of the clay and sterilizing the repository's near-field to depress the deteriorative microbial effects. A quantitative temperature criterion for thermal impact of HLW/SF on clay host rocks is accordingly proposed.

The new mineral species braccoite, ideally NaMn2+5[Si5AsO17(OH)](OH), has been discovered in the Valletta mine dumps, in Maira Valley, Cuneo province, Piedmont, Italy. Its origin is probably related to the reaction between ore minerals and hydrothermal fluids. It occurs as subhedral crystals in brown-red coloured thin masses, with a pale-yellow streak and vitreous to resinous lustre. Braccoite is associated with tiragalloite, for which new data are provided, as well as gamagarite, hematite, manganberzeliite, palenzonaite, quartz, saneroite, tokyoite, unidentified Mn oxides, organic compounds, and Mn arsenates and silicates under study.

Braccoite is biaxial positive with refractive indices α = 1.749(1), β = 1.750(1), γ = 1.760(1). It is triclinic, space group P1̄, with a = 9.7354(4), b = 9.9572(3), c = 9.0657(3) Å, α = 92.691(2), β = 117.057(4), γ = 105.323(3)°, V = 740.37(4) Å3 and Z = 2. Its calculated density is 3.56 g/cm3. The ten strongest diffraction lines of the observed powder X-ray diffraction (XRD) pattern are [d in Å, (I), (hkl)]: 3.055 (69)(22̄1), 3.042 (43)(102), 3.012 (65)(32̄1̄), 2.985 (55)(23̄1̄), 2.825 (100)(213̄), 2.708 (92)(220), 2.627 (43)(23̄2̄), 2.381 (58)(41̄1̄), 2.226 (25)(214̄) and 1.680 (433̄)(36). Chemical analyses by wavelength-dispersive spectroscopy electron microprobe gave (wt.%): Na2O 4.06, CaO 0.05, MnO 41.76, MgO 0.96, Al2O3 0.04, CuO 0.02, SiO239.73, As2O5 6.87, V2O5 1.43, SO3 0.01 and F 0.04. H2O 2.20 was calculated on the basis of 2OH groups p.f.u. Raman spectroscopy confirmed the presence of (SiO4)4–, (AsO4)3– and OH groups. The empirical formula, calculated on the basis of Σ cations-(Na,K) = 11 p.f.u., in agreement with the results of the crystal structure, is Na1.06(Mn2+4.46Mn3+0.32Mg0.19V3+0.01Al0.01Ca0.01)[Si5(As0.48Si0.37V5+0.15)O17(OH)](OH0.98F0.02); the simplified formula is Na(Mn,Mg,Al,Ca)5[Si5(As,V,Si)O17(OH)](OH,F).

Single-crystal XRD allowed the structure to be solved by direct methods and revealed that braccoite is the As-dominant analogue of saneroite. The structure model was refined on the basis of 4389 observed reflections to R1 = 3.47%. Braccoite is named in honour of Dr Roberto Bracco (b. 1959), a systematic minerals collector with a special interest in manganese minerals. The new mineral was approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA 2013-093).

The determination of the crystal structure of benleonardite (P3m1; R = 0.0321 for 1250 reflections and 102 parameters; refined formula Ag15.00Cu1.00Sb1.58As0.42S7.03Te3.97) obtained using data from a gem-quality, untwinned crystal recovered from the type material, revealed that benleonardite exhibits the structure observed for minerals of the pearceite-polybasite group. The structure consists of the stacking of [Ag6(Sb,As)2S6Te]2– A and [Ag9Cu(S,Te)2Te2]2+B layer modules in which (Sb, As) forms isolated SbS3 pyramids typically occurring in sulfosalts; Cu links two (S,Te) atoms with linear coordination, and Ag occupies sites with coordination geometries ranging from quasi-linear to almost triangular. The silver ions are found in the B layer module along two-dimensional diffusion paths and their electron densities are evidenced by means of a combination of a Gram-Charlier development of the atom displacement factors and a split model. In the structure, two S positions are completely replaced by Te (i.e. Te3 and Te4) and one is half occupied [S1: S0.514(9)Te0.486], whereas S2 is completely filled by sulfur. This distribution reflects the crystal-chemical environments of the different cations. On the basis of information gained from this characterization, the crystal-chemical formula of benleonardite was revised according to the structural results, yielding Ag15Cu(Sb,As)2S7Te4 (Z = 1) instead of Ag8(Sb,As)Te2S3(Z = 2) as previously reported. Thus, the mineral must be considered a member of the pearceite-polybasite group. A recalculation of the chemical data listed in the scientific literature for benleonardite according to the structural results obtained here leads to excellent agreement.

Supposed 'merlinoite' crystals from Monte Somma, Vesuvius (Italy) and Fosso Attici, north of Rome (Italy) represent highly twinned coherent intergrowths between merlinoite and phillipsite on a submicroscopic level. The MER (Immm, a ≈ 14.1, b ≈ 14.2, c ≈ 9.9 Å) and PHI (P 21/m, a ≈ 9.9, b ≈ 14.3, c ≈ 8.7 Å, β = 124.8°) frameworks of similar composition are assembled from identical tetrahedral units, though with a different connectivity. Coherent intergrowth and twinning of the two frameworks lead to P42/mnm pseudosymmetry, which is diagnostic of the intergrowth. Under ambient conditions merlinoite has Immm symmetry or I4/mmm if twinned. a low-symmetry model of space group P121/m1 (a ≈ 14.2, b ≈ 14.2, c ≈ 10 Å, β = 90°) allows structure refinement and quantification of the two frameworks.

Upon in situ dehydration to 250°C the evolution of the unit-cell volume of the Monte Somma merlinoite/phillipsite intergrowth displays an intermediate trend between previously studied pure merlinoite from the Khibiny massif (Russia) and Ba-rich phillipsite.

The Monte Somma crystal studied by temperature-dependent single-crystal X-ray diffraction methods also contained a subordinate chabazite inclusion with no coherent structural relationship to the merlinoite/phillipsite framework. Thus, the modification of the chabazite framework on dehydration could also be studied.

The new REE-rich, monoclinic, epidote-supergroup minerals ferriakasakaite-(La) and ferriandrosite-(La), found in tephroite calcite veinlets cutting the stratiform ferromanganese deposit from the Shobu area, Ise City, Mie Prefecture, Japan, were studied using electron microprobe analysis and single-crystal X-ray diffraction methods. Ferriakasakaite-(La), ideally A1CaA2LaM1Fe3+M2AlM3Mn2+(SiO4)(Si2O7)O(OH) (Z = 2, space group P21/m), has a new combination of dominant cations at A1(Ca) and M3(Mn2+), which are the key sites to determine a root name for epidote-supergroup minerals. The unit-cell parameters are a = 8.8733(2), b = 5.7415(1), c = 10.0805(3) Å, β = 113.845(2)° and V = 469.73(2) Å3. According to the structural refinement (R1 = 3.13%), the determined structural formula is A1(Ca0.54Mn2+0.46)A2[(La0.48Ce0.20Pr0.07Nd0.18Gd0.02)Σ0.95Ca0.05]M1(Fe0.423+V0.343+Al0.18Ti0.064+)M2(Al0.96Fe0.043+)M3(Mn0.502+Fe0.432+Mg0.07)(SiO4)(Si2O7)O(OH). Ferriandrosite-(La), ideally A1Mn2+A2LaM1Fe3+M2AlM3Mn2+(SiO4)(Si2O7)O(OH) (Z = 2, space group P21/m), is the M1Fe3+ analogue of androsite. The unit-cell parameters are a = 8.8779(1), b = 5.73995(1), c = 10.0875(2) Å, β = 113.899(1)° and V = 469.97(2) Å3, and the structural formula is A1(Mn0.562+Ca0.44)A2[(La0.49Ce0.20Pr0.08Nd0.19Gd0.02)Σ0.97Ca0.03]M1(Fe0.403+V0.283+Al0.20Fe0.052+Ti0.074+)M2(Al0.97Fe0.033+)M3(Mn0.502+Fe0.402+Mg0.10)(SiO4)(Si2O7)O(OH) (R1 = 2.93%). The two new minerals, which are compositionally very similar overall, are distinguished by occupancy of A1, Ca vs. Mn2+. The structural properties of these minerals depend not only on the REE content at A2, but also on the Mn content at A1.