Pilawite-(Y), ideally Ca2(Y,Yb)2Al4(SiO4)4O2(OH)2, was discovered in a pegmatite near Piława Górna, Lower Silesia, Poland. The mineral occurs as white, translucent, brittle crystals up to 1.5 mm in size. It has a white streak, vitreous lustre and a hardness of 5 on Mohs scale. The calculated density is 4.007 g/cm3. Pilawite-(Y) is non-pleochroic, biaxial (+), with refractive indices α = 1.743(5), β = 1.754(5) and γ = 1.779(5), birefringence Δ = 0.03–0.04, 2Vmeas. = 65(2)° and 2Vcalc. = 68°. Pilawite-(Y) is monoclinic P21/c, with unit-cell parameters a = 8.558(3) Å, b = 7.260(3) Å, c = 11.182(6) Å, β = 90.61(4)o, V = 694.7(4) Å3. The crystal structure was refined to an R1 index of 2.76% and consists of chains of edge- and corner-sharing octahedra decorated by tetrahedra and having the stoichiometry [Al2(SiO4)4O(OH)] that link by sharing corners to form an octahedron–tetrahedron framework with large interstices that contain Ca2+ and (Y,Ln)3+. It is a graphical isomer of the Al–P framework in palermoite, Sr2Li4[Al2(PO4)2(OH)2]2. The pilawite-(Y)-bearing assemblage began crystallization at high Y + Ln activities and was modified progressively by a Ca-enriched fluid, resulting in the sequence: keiviite-(Y) → gadolinite-(Y) to hingganite-(Y) + hellandite-(Y) → pilawite-(Y) → allanite-(Y) → epidote/zoisite.

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.

Fluor-tsilaisite, NaMn3Al6(Si6O18)(BO3)3(OH)3F, is a new mineral of the tourmaline supergroup. It occurs in an aplitic dyke of a LCT-type pegmatite body from Grotta d'Oggi, San Piero in Campo, Elba Island, Italy, in association with quartz, K-feldspar, plagioclase, elbaite, schorl, fluor-elbaite and tsilaisite. Crystals are greenish yellow with a vitreous lustre, sub-conchoidal fracture and white streak. Fluor-tsilaisite has a Mohs hardness of ∼7 and a calculated density of 3.134 g/cm3. In plane-polarized light, fluor-tsilaisite is pleochroic (O = pale greenish yellow and E = very pale greenish yellow), uniaxial negative. Fluor-tsilaisite is rhombohedral, space group R3m, a = 15.9398(6), c = 7.1363(3) Å, V = 1570.25(11) Å3, Z = 3. The crystal structure of fluor-tsilaisite was refined to R1 = 3.36% using 3496 unique reflections collected with MoKα X-ray intensity data. Crystal-chemical analysis resulted in the empirical formula: X(Na0.69〈0.29Ca0.02)Σ1.00Y(Mn2+1.29Al1.21Li0.56Ti0.03)Σ6.00ZAl6T(Si5.98Al0.03)Σ6.00B2.92O27V(OH)3W[F0.39(OH)0.25O0.36]Σ1.00.

Comparisons were performed between fluor-tsilaisite and a tsilaisitic tourmaline from the same locality as the holotype specimen. This latter tourmaline sample was selected for this study due to its remarkable composition (MnO = 11.63 wt.%), the largest Mn content found in tourmaline so far.

Fluor-tsilaisite is related to tsilaisite through the substitution WF ↔ W(OH) and with fluor-elbaite through the substitution Y(Al + Li) ↔ 2YMn2+, and appears to be a stepwise intermediate during tourmaline evolution from tsilaisite to fluor-elbaite.

The crystal structure of the mineral koninckite was solved from synchrotron powder X-ray diffraction (XRD) data and refined using density-functional theory (DFT) calculations. Koninckite is tetragonal, with the space group P41212, a = 11.9800(5) Å, c = 14.618(1) Å, V = 2097.9(2) Å3, Z = 8. Its structure is a heteropolyhedral framework with zeolite-like tunnels along [001]. Owing to the severe peak overlap in the powder XRD data and the probable intergrowth of enantiomorphic domains in koninckite, the DFT calculations were applied to provide precise atomic positions (including hydrogen). Additionally, the DFT calculations suggest strongly that koninckite is an antiferromagnetic semiconductor, at least at low temperatures. The DFT computations were used to locate H2O molecules in the channels and to complete the structural description. Thermogravimetric analysis and powder XRD data at variable temperatures show that the structure of koninckite dehydrates and eventually collapses between 160–180°C. Negative thermal expansion was observed between 80 and 150°C. A list of the known occurrences of koninckite suggests that this mineral is not as rare as assumed previously; koninckite is often fine-grained, inconspicuous, and thereby easy to overlook. Koninckite is yet another natural example of an Fe-phosphate zeolitic material.

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-].

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.

The crystal structure of synthetic Ni-rich tourmaline with a nickel content of 18.96 wt.% NiO (a = 15.890(2), c = 7.1815(8) Å) has been refined to R = 3.1% using single-crystal X-ray diffraction data. It has been shown that Ni is distributed not only over the Y, but also over the Z sites according to the ideal formula Na(Ni22+Al)(Al5Ni2+)(Si6O18)(BO3)3(OH)4. Based on bond valences and charge balance analysis it has been shown that this composition corresponds to the stable disordered member of the solid solution series NaAl3Al6(Si6O18)(BO3)3(O)3(OH) NaNi32+Al6(Si6O18)(BO3)3(OH)4.

Taking into consideration available structural data on Me2+ (Ni, Cu, Co, Fe, Mn)-rich tourmalines, cation-size mismatch and bond-valence calculations we assume that there are no structural constraints precluding occurrence of these cations in both octahedral sites. Divalent transitional metal-rich tourmalines have not been found in Nature probably due to the insufficient concentration of these elements in B-rich geological systems.

The high-temperature- and moisture-dependent behaviour of synthetic kanemite (NaSi2O4(OH)·3H2O or SKS-10) has been studied by in situ powder X-ray diffraction. Heating experiments in the range between ambient temperatures and 250°C confirm earlier investigations that the dehydration of kanemite occurs in two steps. According to our results the two different reactions start at ∼30 and 75°C. The dehydration products have the following compositions: NaSi2O4(OH)·H2O (monohydrate) and NaSi2O4(OH), respectively. The crystal structures of both phases have been solved at ambient conditions ab initio from laboratory powder diffraction data using samples that have been carefully dehydrated at 60 and 150°C, respectively, and refined subsequently by the Rietveld method. Basic crystallographic data are as follows: NaSi2O4(OH)·H2O: orthorhombic, space group Pna21, a = 7.2019(1), b = 15.3252(2), c = 4.8869(1) Å, V = 539.37(1) Å3, Z = 4; NaSi2O4(OH): monoclinic, space group P21, a = 6.3873(1), b = 4.8876(1), c = 7.1936(1) Å, β = 93.36(1)°, V = 224.19(1) Å3, Z = 2. Both compounds belong to the group of single-layer silicates based on Si2O4 (OH) sheets. The sodium cations are located between the tetrahedral sheets and are surrounded by oxygen atoms from silicate anions and/or water molecules. Depending on the dehydration step the coordination numbers of the alkali ions vary between six (kanemite) and five (NaSi2O4(OH)). Kanemite and its two dehydration products show structural similarities which are discussed in detail. Moisture-dependent diffraction studies at ambient temperatures indicate that kanemite is stable between 10% and at least 90% relative humidity. Below the lower threshold a transformation to the monohydrate phase was observed. Dehydration and rehydration as a function of humidity is reversible. However, this process is combined with a significant loss of crystallinity of the samples.

Marécottite, ideally Mg3[(UO2)4O3(OH)(SO4)2]2(H2O)28, a triclinic, Mg-dominant member of the zippeite group, was described originally from a small uranium deposit at La Creusaz in Wallis (Switzerland). It has recently been found at Jáchymov (Czech Republic), where it forms exceptional crystals, up to 0.3 mm across. According to an electron microprobe study of these crystals, marécottite from Jáchymov is chemically similar to the material from the La Creusaz deposit. However, the Jáchymov crystals exhibit more cation substitution (Zn2+ and Mn2+ for Mg2+). The chemical composition of marécottite from Jáchymov corresponds to the empirical formula [(Na0.05K0.07)Σ0.12(Mg1.83Zn0.41Mn0.41Cu0.15Ni0.08)Σ2.88Al0.07]Σ3.07(UO2)8[(SO4)3.77(SiO4)0.21]Σ3.98O6(OH)1.84·28H2O (the mean of four representative spots; calculated on the basis of eight U atoms and 28 H2O per formula unit and 1.84 OH for charge balance). According to single-crystal X-ray diffraction, marécottite from Jáchymov is triclinic, P1, a = 10.8084(2), b = 11.2519(3), c = 13.8465(3) Å, α = 66.222(2), β = 72.424(2), γ = 70.014(2)o, V = 1421.57(6) Å3 and Z = 1. The crystal structure was refined from a highly redundant dataset (30,491 collected reflections) to R1 = 0.0367 for all 7042 unique reflections. The refined structure confirms the previously determined structure for the crystal from the La Creusaz deposit. An extensive network of hydrogen bonds is an important feature that keeps the whole structure together, but the positions of H atoms had not been determined previously. The H-bond scheme proposed based on a detailed bond-valence analysis and the role of different types of molecular H2O in the structure is discussed.

One of the most challenging aspects of understanding the flow of gas and water during testing in clay-rich low-permeability materials is the difficulty in visualizing localized flow. Whilst understanding has been increased using X-ray Computed-tomography (CT) scanning, synchrotron X-ray imaging and Nuclear Magnetic Resonance (NMR) imaging, real-time testing is problematic under realistic in situ conditions confining pressures, which require steel pressure vessels. These methods tend not to have the nano-metre scale resolution necessary for clay mineral visualization, and are generally not compatible with the long duration necessary to investigate flow in such materials. Therefore other methods are necessary to visualize flow paths during post-mortem analysis of test samples. Several methodologies have been established at the British Geological Survey (BGS), in order to visualize flow paths both directly and indirectly. These include: (1) the injection of fluorescein-stained water or deuterium oxide; (2) the introduction of nanoparticles that are transported by carrier gas; (3) the use of radiologically tagged gas; and (4) the development of apparatus for the direct visualization of clay. These methodologies have greatly increased our understanding of the transport of water and gas through intact and fractured clay-rich materials. The body of evidence for gas transport through the formation of dilatant pathways is now considerable. This study presents observations using a new apparatus to directly visualize the flow of gas in a kaolinite paste. The results presented provide an insight into the flow of gas in clay-rich rocks. The flow of gas through dilatant pathways has been shown in a number of argillaceous materials (Angeli et al., 2009; Autio et al., 2006; Cuss et al., 2014; Harrington et al., 2012). These pathways are pressure induced and an increase in gas pressure leads to the dilation of pathways. Once the gas breakthrough occurs, pressure decreases and pathways begin to close. This new approach is providing a unique insight into the complex processes involved during the onset, development and closure of these dilatant gas pathways.

Flurlite, ideally Zn3Mn2+Fe3+(PO4)3(OH)2·9H2O, is a new mineral from the Hagendorf-Süd pegmatite, Hagendorf, Oberpfalz, Bavaria, Germany. Flurlite occurs as ultrathin (<1 μm) translucent platelets that form characteristic twisted accordion-like aggregates. The colour varies from bright orange red to dark maroon red. Cleavage is perfect parallel to (001). The mineral occurs on mitridatite and is closely associated with plimerite. Other associated minerals are beraunite, schoonerite, parascholzite, robertsite and altered phosphophyllite. The calculated density of flurlite is 2.84 g cm–3. It is optically biaxial (–), α = 1.60(1), β= 1.65(1) and γ = 1.68(1), with weak dispersion and parallel extinction, X ≈ c, Y ≈ a, Z ≈ b. Pleochroism is weak, with colours: X = pale yellow, Y = pale orange, Z = orange brown. Electron microprobe analyses (average of seven) with FeO and Fe2O3 apportioned and H2O calculated on structural grounds, gave ZnO 25.4, MnO 5.28, MgO 0.52, FeO 7.40, Fe2O3 10.3, P2O5 27.2, H2O 23.1, total 99.2 wt.%. The empirical formula, based on 3 P a.p.f.u. is Zn2.5Mn2+0.6Fe2+0.8Mg0.1Fe3+(PO4)3(OH)2·9H2O. Flurlite is monoclinic, P21/m, with the unit-cell parameters (at 100 K) of a = 6.3710(13), b = 11.020(2), c = 13.016(3) Å, β = 99.34 (3)°. The strongest lines in the X-ray powder diffraction pattern are [dobs in Å(I) (hkl)] 12.900(100)(001); 8.375(10)(011); 6.072(14)(101); 5.567(8)(012); 4.297(21)(003); 2.763(35)(040). Flurlite (R1 = 0.057 for 995 F > 4σ(F)) has a heteropolyhedral layer structure, with layers parallel to (001) and with water molecules packing between the layers. The slab-like layers contain two types of polyhedral chains running parallel to [100]: (a) chains of edge-sharing octahedra containing predominantly Zn and (b) chains in which Fe3+-centred octahedra share their apices with dimers comprising Zn-centred trigonal bipyramids sharing an edge with PO4 tetrahedra. The two types of chains are interconnected by corner-sharing along [010]. A second type of PO4 tetrahedron connects the chains to MnO2(H2O)4 octahedra along [010] to complete the structure of the (001) slabs. Flurlite has the same stoichiometry as schoonerite, but with dominant Zn rather than Fe2+ in the edge-shared chains. Schoonerite has a similar heteropolyhedral layer structure with the same layer dimensions 6.4 × 11.1 Å. The different symmetry (orthorhombic, Pmab) for schoonerite reflects a different topology of the layers.

Ferribushmakinite (IMA2014-055), Pb2Fe3+(PO4)(VO4)(OH), the Fe3+ analogue of bushmakinite, is a new mineral from the Silver Coin mine, Valmy, Iron Point district, Humboldt County, Nevada, USA, where it occurs as a low-temperature secondary mineral in association with plumbogummite, mottramite, Br-rich chlorargyrite and baryte on massive quartz. Ferribushmakinite forms yellow slightly flattened prisms up to 0.2 mm long growing in X and sixling twins. The streak is pale yellow. Crystals are translucent and have adamantine lustre. The Mohs hardness is ∼2, the tenacity is brittle, the fracture is irregular to splintery and crystals exhibit one or two fair cleavages in the [010] zone. The calculated density is 6.154 g/cm3. Electron microprobe analyses provided: PbO 63.69, CaO 0.07, CuO 1.11, Fe2O3 7.63, Al2O3 1.63, V2O5 12.65, As2O5 3.09, P2O58.63, H2O 1.50 (structure), total 100.00 wt.% (normalized). The empirical formula (based on nine O a.p.f.u.) is: (Pb1.99Ca0.01)Σ2.00(Fe0.66Al0.22Cu0.10)Σ0.98(V0.97P0.85As0.19)Σ2.01O7.84(OH)1.16. Ferribushmakinite is monoclinic, P21/m, a = 7.7719(10), b = 5.9060(7), c = 8.7929(12) Å, β = 111.604(8)°, V = 375.24(9) Å3 and Z = 2. The eight strongest lines in the powder X-ray diffraction pattern are [dobs in Å (I)(hkl)]: 4.794(46)(011); 3.245(84)(211); 2.947(100)(020,212,103); 2.743(49)(112); 2.288(30)(220); 1.8532(27)(314,403); 1.8084(27)(multiple); and 1.7204(28)(312,114,321). Ferribushmakinite is a member of the brackebuschite supergroup. Its structure (R1 = 3.83% for 577 Fo > 4σF) differs from that of bushmakinite only in the dominance of Fe3+ over Al in the octahedral site.

Iodine-129 is a high-yield fission product formed in nuclear reactors and is a risk-driving radionuclide in both contaminated land and radioactive waste disposal due to its high mobility and long half-life. Here, the bioreduction behaviour of iodate was investigated by tracking iodine speciation and concentration in solution during the development of progressive anoxia in sediment microcosm experiments incubated at neutral pH. Experiments with acetate added as an electron donor showed the expected cascade of terminal electron-accepting processes. Analysis of solution chemistry showed reduction of iodate to iodide during the early stages of metal (Mn(IV) and Fe(III)) reduction, but with no significant retention of iodine species on solids. There was, however, a net release of natural iodine associated with the sediments to solution when robust iron reduction / sulfate reduction had developed. In addition, over 210 days, the controls with no electron donor and the sterile controls showed no Mn(IV) or Fe(III) reduction but displayed modest sorption of iodate to the sediments in the absence of bioreduction. Overall these results show that under oxic conditions iodate may be partially sorbed to sediments over extended periods but that development of mildly reducing conditions leads to the reductive release of iodine to solution as iodide.

Bonazziite is a new mineral from Khaidarkan deposit, Kyrgyzstan and represents the natural analogue of the β-form of the well known As4S4 compound. It occurs as rare crystals up to 100 μm across associated with realgar, sulfur, wakabayashilite, alacránite, non-stoichiometric As4S4+x sulfides and stibnite in a calcite matrix. In thick section, bonazziite is opaque with a resinous lustre and a dark-orange streak. It is brittle; the Vickers hardness (VHN15) is 70 kg/mm2 (range: 60–76) (Mohs hardness of ∼2½). In plane-polarized incident light, bonazziite is strongly bireflectant and pleochroic from orange to light red. The mineral shows orange to red internal reflections. Between crossed polars, the mineral is strongly anisotropic with greyish to light-blue rotation tints. Reflectance percentages in air for Rmin and Rmax are 19.9, 22.2 (471.1 nm), 19.1, 21.3 (548.3 nm), 18.8, 19.7 (586.6 nm) and 17.8, 18.9 (652.3 nm), respectively. Bonazziite is monoclinic, space group C2/c, with a = 9.956(1), b = 9.308(1), c = 8.869(1) Å, β = 102.55(2)° and V = 802.3(2) Å3, Z = 4. The crystal structure [R1 = 0.0263 for 735 reflections with Fo > 4σ(Fo)] is based on the As4S4 cage-like molecule, in which each As atom links one As and two S atoms. The As4S4 molecule is identical to that found in the structure of realgar. The six strongest powder diffraction lines [d in Å (I/I0) (hkl)] are: 5.74 (100) (1̄11); 4.10 (60) (021); 3.92 (50) (1̄12); 3.12 (60) (022, 310); 2.95 (50) (221, 202); 2.86 (80) (2̄22, 1̄31). a mean of six electron microprobe analyses gave the formula As3.95S4.05, on the basis of eight atoms. The new mineral has been approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA No. 2013-141) and named for Paola Bonazzi, in recognition of her seminal contributions to the study of arsenic sulfides and their alteration induced by exposure to light.

The new mineral campostriniite, (Bi3+,Na)3(NH4,K)2Na2(SO4)6·H2O, was found in an active fumarole (fumarole FA, temperature ∼350°C) at La Fossa Crater, Vulcano, Aeolian Islands, Sicily, Italy. It occurs on a pyroclastic breccia as white prismatic crystals up to 0.2 mm long, in association with adranosite, demicheleite-(Br), demicheleite-(I), argesite and sassolite. The mineral is monoclinic, space group: C2/c (no. 15) with a = 17.748(3), b = 6.982(1) c = 18.221(3) Å, β = 113.97(1)°, V = 2063(1) Å3 and Z = 4. The six strongest reflections in the powder X-ray diffraction pattern are: [dobs in Å (I)(hkl)] 6.396(100)(110), 7.507(75)(202), 2.766(60)(316), 3.380(57)(312), 5.677(55)(111), 3.166(50)(4 0 2). The empirical formula (based on 25 anions p.f.u.) is Bi2.41N1.52Na2.41K0.48 S6.07H8.08O25. The calculated density is 3.87 g cm–3. Using single-crystal diffraction data, the structure was refined to a final R(F) = 0.051 for 3025 independent observed reflections [I > 2σ(I)]. Campostriniite is isostructural with görgeyite and belongs to the 7.CD group of the Strunz classification system. The structure contains two independent nine-fold coordinated sites, one of them located on a two-fold axis (M1) and the other one in general position (M2) essentially occupied by Bi3+ atoms and minor amounts of Na+ ions, an eight-fold coordinated site fully occupied by Na +ions and another eight-fold coordinated site occupied by NH+4 and K+ ions; three independent sulfate anions in a general position and a water molecule coordinated to M1 and located on a two-fold axis are also present.

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.

Geological disposal facilities (GDF) are intended to isolate and contain radioactive waste within multiple protective barriers, deep underground, to ensure that no harmful quantities of radioactivity reach the surface environment. The last line of defense in a multi-barrier GDF is the geosphere, where iron is present in the host rock mineralogy as either Fe(II) or Fe(III), and in groundwater as Fe(II) under reducing conditions. The mobility of risk-driving radionuclides, including uranium and technetium, in the environment is affected significantly by their valence state. Due to its low redox potential, Fe(II) can mediate reduction of these radionuclides from their oxidized, highly mobile, soluble state to their reduced, insoluble state, preventing them from reaching the biosphere. Here a study of five types of potential host rocks, two granitoids, an andesite, a mudstone and a clay-rich carbonate, is reported. The bulk rocks and their minerals were analysed for iron content, Fe(II/III) ratio, and for the speciation and fine-grained nature of alteration product minerals that might have important controls on groundwater interaction. Total iron content varies between 0.9% in clays to 5.6% in the andesite. X-ray absorption spectroscopy reveals that Fe in the granitoids and andesite is predominantly Fe(II), and in mudstones, argillaceous limestone and terrestrial sandstone is predominantly Fe(III). The redox reactivity of the potential host rocks both in the presence and absence of Fe(II)-containing 'model' groundwater was investigated using an azo dye as a probe molecule. Reduction rates as determined by reactivity with the azo dye were correlated with the ability of the rocks to uptake Fe(II) from groundwater rather than with initial Fe(II) content. Potential GDF host rocks must be characterized in terms of mineralogy, texture, grain size and bulk geochemistry to assess how they might interact with groundwater. This study highlights the importance of redox reactivity, not just total iron and Fe(II)/(III) ratio, when considering the host rock performance as a barrier material to limit transport of radionuclides from the GDF.