Fassinaite, ideally Pb22+(S2O3)(CO3), is a new mineral from the Trentini mine, Mount Naro, Vicenza Province, Veneto, Italy (holotype locality). It is also reported from the Erasmus adit, Schwarzleo District, Leogang, Salzburg, Austria and the Friedrich-Christian mine, Schapbach, Black Forest, Baden-Wurttemberg, Germany (cotype localities). At the Italian type locality it occurs as acicular [010]. colourless crystals up to 200 μn long, closely associated with galena, quartz and anglesite. At the Austrian cotype locality it is associated with cerussite, rare sulphur and very rare phosgenite. At the German cotype locality anglesite is the only associated phase. Fassinaite crystals commonly have flat chisel-shaped terminations. They are transparent with vitreous to adamantine lustre and a white streak. Fassinaite is brittle with an irregular fracture and no discernible cleavage; the estimated Mohs hardness is 11/2—2. The calculated density for the type material is 6.084 g cm–3 (on the basis of the empirical formula), whereas the X-ray density is 5.947 g cm–3. In common with other natural lead thiosulphates (i.e. sidpietersite and steverustite) fassinaite has intense internal reflections, which do not allow satisfactory optical data to be collected; the crystals are length-slow and have very high birefringence. The mineral is not fluorescent.

Fassinaite is orthorhombic, space group Pnma, with unit-cell parameters (for the holotype material) a = 16.320(2), b = 8.7616(6), c = 4.5809(7) Å, V = 655.0(1) Å3, a:b:c = 1.863:1:0.523, Z = 4. Single-crystal structural studies were carried out on crystals from all three localities: R1(F) values range between 0.0353 and 0.0596. The structure consists of rod-like arrangements of Pb-centred polyhedra that extend along the [010] direction. These ‘rods’ are linked, alternately, by (CO3)2– and (S2O3)2– groups. The (S2O3)2– groups point alternately left and right (in a projection on [001] with [010] set vertical) if the apex occupied by the S2– in the thiosulphate group is defined to be the atom giving the direction. The lead atoms are nine-coordinated by seven oxygen atoms and two sulphur (S2–) atoms. The eight strongest X-ray powder-diffraction lines [d in Å (I/I0) (hkl)] are: 4.410 (39) (101), 4.381 (59) (020), 4.080 (62) (400), 3.504 (75) (301), 3.108 (100) (121), 2.986 (82) (420), 2.952 (49) (221) and 2.736 (60) (321). Electron-microprobe analyses produce an empirical formula Pb2.01(1)(S1.82(2)O3)CO3 (on the basis of six oxygen atoms). The presence of both carbonate and thiosulphate groups was corroborated by Raman spectra, which are discussed in detail. Fassinaite is named after Bruno Fassina (b. 1943), an Italian mineral collector who discovered the mineral in 2009.

Nordgauite, MnAl2(PO4)2(F,OH)2·5H2O, is a new secondary phosphate from the Hagendorf-Süd pegmatite, Bavaria, Germany. It occurs as white to off-white compact waxy nodules and soft fibrous aggregates a few millimetres across in altered zwieselite—triplite. Individual crystals are tabular prismatic, up to 200 μ long and 10 μ wide. Associated minerals include fluorapatite, sphalerite, uraninite, a columbite—tantalite phase, metastrengite, several unnamed members of the whiteite—jahnsite family, and a new analogue of kingsmountite. The fine-grained nature of nordgauite meant that only limited physical and optical properties could be obtained; streak is white; fracture, cleavage and twinning cannot be discerned. Dmeas. and Dcaic. are 2.35 and 2.46 g cm–3, respectively; the average RI is n = 1.57; the Gladstone-Dale compatibility is —0.050 (good). Electron microprobe analysis gives (wt.%): CaO 0.96. MgO 0.12, MnO 14.29, FeO 0.60, ZnO 0.24, A12O3 22.84, P2O5 31.62, F 5.13 and H2O 22.86 (by CHNX less F=O 2.16, total 96.50. The corresponding empirical formula is (Mn0.90Ca0.08Fe0.04Zn0.01Mg0.01)-Σi.04Ai2.0i(PO4)2[F1.21,(OH)0.90]Σ2.11·5.25H2O. Nordgauite is triclinic, space group P1̄, with the unit-cell parameters: a = 9.920(4), b = 9.933(3), c = 6.087(2) Å, α = 92.19(3), β = 100.04(3), γ = 97.61(3)°, V = 584.2(9) Å3 and Z = 2. The strongest lines in the XRD powder pattern are [d in Å (I) (hkl)] 9.806 (100)(010), 7.432 (40)(l1̄0), 4.119 (20)(210), 2.951 (16)(031), 4.596 (12)(21̄O), 3.225 (12)(220) and 3.215 (12)(121). The structure of nordgauite was solved using synchrotron XRD data collected on a 60 μm × 3 μm × 4 μm needle and refined to R1 = 0.0427 for 2374 observed reflections with F > 4σ(F). Although nordgauite shows stoichiometric similarities to mangangordonite and kastningite, its structure is more closely related to those of vauxite and montgomeryite in containing zig-zag strings of corner-connected Al-centred octahedra along [011], where the shared corners are alternately in cis and trans configuration. These chains link through corner-sharing with PO4 tetrahedra along [001] to form (100) slabs that are interconnected via edge-shared dimers of MnO6 polyhedra and other PO4 tetrahedra.

Taking advantage of the bent uranyl-peroxide-uranyl interaction found in studtite, 26 nanoscale clusters have been synthesized using uranyl hexagonal bipyramids. Sixteen of these clusters are built from uranyl hexagonal bipyramids only. Eight contain pyrophosphate groups that bridge between uranyl polyhedra, and two contain oxalate groups that adopt a similar structural role. These clusters contain from 20 to 60 uranyl polyhedra and have diameters in the range ∼1.5 to 3 nm. All spontaneously selfassemble in aqueous solution under ambient conditions.

Megawite is a perovskite-group mineral with an ideal formula CaSnO3 that was discovered in altered silicate-carbonate xenoliths in the Upper Chegem caldera, Kabardino-Balkaria, Northern Caucasus. Russia. Megawite occurs in ignimbrite, where it forms by contact metamorphism at a temperature >800°C and low pressure. The name megawite honours the British crystallographer Helen Dick Megaw (1907—2002) who did pioneering research on perovskite-group minerals. Megawite is associated with spurrite, reinhardbraunsite, rondorfite, wadalite, srebrodolskite, lakargiite, perovskite, kerimasite. elbrusite-(Zr), periclase, hydroxylellestadite, hydrogrossular, ettringite-group minerals, afwillite. hydrocalumite and brucite. Megawite forms pale yellow or colourless crystals up to 15 urn on edge with pseudo-cubic and pseudo-cuboctahedral habits. The calculated density and average refractive index are 5.06 g cm–3 and 1.89, respectively. Megawite is Zr-rich and usually crystallizes on lakargiite. CaZrO3. The main bands in the Raman spectrum of megawite are at: 159, 183, 262, 283, 355, 443. 474, 557 and 705 cm–1. The unit-cell parameters and space group of megawite, derived from electron back scattered diffraction, are: a = 5.555(3), b = 5.708(2), c = 7.939(5) Å, V = 251.8(1) Å3, Pbnm, Z = 4; they are based on an orthorhombic structural model for the synthetic perovskite CaSn0.6Zr0.4O3.

The type specimen of peisleyite has been reinvestigated by a combination of scanning electron microscopy, electron probe microanalysis (EPMA) and synchrotron powder X-ray diffraction. Morphological investigation showed that mats of peisleyite crystals, individually <3 μm across, are intergrown with wavellite veinlets to form the white cryptocrystalline material that is typical of ‘peisleyite’. New EPMA data (mean of 12 analyses) gave the empirical formula of peisleyite as (Na1.69Ca0.18)Σ1.87(Al9.04Fe0.03)Σ9.07[(P6.28S1.38Si0.25)O4]Σ7.91(OH)6.66·27.73H2O, or ideally Na2Al9[(P,S)O4]8(OH)6·28H2O. The associated wavellite was found to be F-rich. Synchrotron powder data were indexed and refined and gave the following unit cell: P1̄, a = 9.280(19), b = 11.976(19), c = 13.250(18) Å, α = 91.3(1), β = 75.6(1), γ = 67.67(1)°, V = 1308(5) Å3 and Z = 4. These data are significantly different to those reported in the original description of peisleyite.

During the past 70 years, more than 2000 metric tonnes of Pu, and substantial quantities of the ‘minor’ actinides such as Np, Am and Cm, have been generated in nuclear reactors. Some of these transuranium elements can be a source of energy in fission reactions (e.g. 239Pu), a source of fissile material for nuclear weapons (e.g. 239Pu and 2Np), and of environmental concern because of their long half-lives and radiotoxicity (e.g. 239Pu and 237Np). There are two basic strategies for the disposition of these transuranium elements: (1) to ‘burn’ or fission the actinides using nuclear reactors or accelerators; (2) to dispose of the actinides directly as spent nuclear fuel or to ‘sequester’ the actinides in chemically durable, radiation-resistant materials that are also suitable for geological disposal. For the latter strategy, there has been substantial interest in the use of actinide-bearing minerals, especially isometric pyrochlore, A2B2Oi (A = rare earths; B = Ti, Zr, Sn, Hf), for the immobilization of actinides, particularly plutonium, both as inert matrix fuels and nuclear waste forms. Systematic studies of rare-earth pyrochlores have led to the discovery that certain compositions (B = Zr, Hf) are stable to very high doses of α-decay event damage. Recent developments in the understanding of the properties of actinide-bearing solids have opened up new possibilities for the design of advanced nuclear materials that can be used as fuels and waste forms. As an example, the amount of radiation damage that accumulates over time can be controlled by the selection of an appropriate composition for the pyrochlore and a consideration of the thermal environment of disposal. In the case of deep borehole disposal (3—5 km), the natural geothermal gradient may provide enough heat to reduce the amount of accumulated radiation damage by thermal annealing.

The accurate measurement of trace element concentrations in natural sulphides by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been limited by the lack of matrix-matched calibration standards. The synthesis of a standard, IMER-1, by incorporating four minor and 34 trace elements into a chalcogenide glass matrix Ge28Sb12S60 is reported here. Chemical analysis by electron probe microanalysis (EPMA), LA-ICP-MS, solution ICP-MS, and inductively coupled plasma-optical emission spectroscopy (ICP-OES) confirmed the excellent homogeneity of major elements (1-σ relative standard deviation (RSD) <1% for S, Sb and Ge) and acceptable homogeneity of most trace elements (1-σ RSD <10%). The standard was validated by analysing trace-elements concentrations in three geological pyrite specimens using IMER-1 as the calibration standard and comparing the results to previously reported values also determined by LA-ICP-MS but using a different calibration standard. STDGL2b-2. The results suggest that IMER-1 may be an appropriate calibration standard for LA-ICP-MS analysis of trace elements in natural sulphides.

The relative stabilities of the copper/zinc solid solutions of hydroxyl sulphates, carbonates, nitrates, chlorides and bromides were studied by attempting their preparation using a variety of methods. All of the naturally occurring solid solutions except rosasite were obtained as single phases. Rosasite crystallized in a mixture with malachite and calcium carbonate during a room temperature preparation from calcium carbonate, copper nitrate and zinc nitrate. The solid solution with the antlerite stoichiometry [endmember Cu3SO4(OH)4] as well as the nitrates were not produced by the methods employed. All of the natural polymorphs of Cu2(OH)3Cl were obtained and a new method for the preparation of botallackite is reported. Botallackite was found to be stable in solution for over a year, contrary to previous reports. A bromine-bearing analogue of botallackite was prepared. Compounds were characterized by X-ray diffractometry, which was used to determine the unit-cell parameters, and by atomic absorption spectroscopy. The relative instability of solid solutions with certain stoichiometries is discussed in terms of the Jahn-Teller effect and relative solubilities.

Bêhounekite, orthorhombic U(SO4)2(H2O)4, is the first natural sulphate of U4+. It was found in the Geschieber vein, Jáchymov (St Joachimsthal) ore district, Western Bohemia, Czech Republic, crystallized on the altered surface of arsenic and associated with kaatialaite, arsenolite, claudetite, unnamed phase UM1997-20-AsO:HU and gypsum. Bêhounekite most commonly forms short-prismatic to tabular green crystals, rarely up to 0.5 mm long. The crystals have a strong vitreous lustre and a grey to greenish grey streak. They are brittle with an uneven fracture and have very good cleavage along ﹛100﹜. The Mohs hardness is about 2. The mineral is not fluorescent either in short- or long-wavelength UV radiation. Bêhounekite is moderately pleochroic, α∼β is pale emerald green and γ is emerald green, and is optically biaxial (+) with α = 1.590(2), β = 1.618(4), γ = 1.659(2) (590 nm), 2V (calc.) = 81°, birefringence 0.069. The empirical formula of bêhounekite (based on 12 O atoms, from an average of five point analyses) is (U0.99Y0.03)Σ1.02(SO4)1.97(H2O)4. The simplified formula is U(SO4)2(H2O)4, which requires UO2 53.77. SO3 31.88, H2O 14.35, total 100.00 wt.%. Bêhounekite is orthorhombic, space group Pnma, a = 14.6464(3), b = 11.0786(3), c = 5.6910(14) Å, V = 923.43(4) Å3, Z = 4, Dcalc = 3.62 g cm–3. The seven strongest diffraction peaks in the X-ray powder diffraction pattern are [dobs in Å (I) (hid)]: 7.330 (100) (200), 6.112 (54) (210), 5.538 (21) (020), 4.787 (42) (111), 3.663 (17) (400), 3.478 (20) (410), 3.080 (41) (321). The crystal structure of bêhounekite has been solved by the charge-flipping method from single-crystal X-ray diffraction data and refined to R1 = 2.10 % with a GOF = 1.51, based on 912 unique observed diffractions. The crystal structure consists of layers built up from [8]-coordinate uranium atoms and sulphate tetrahedra. The eight ligands include four oxygen atoms from the sulphate groups and four oxygen atoms from the H2O molecules. Each uranium coordination polyhedron is connected via sulphate tetrahedra with other uranium polyhedra and through hydrogen bonds to the apices of sulphate tetrahedra. The dominant features of the Raman and infrared spectra of bêhounekite are related to stretching vibrations of SO4 tetrahedra (∼1200–950 cm–1), O-H stretching modes (∼3400–3000 cm–1) and H—O—H bending modes (∼1650 cm–1). The mineral is named in honour of František Bêhounek, a well known Czech nuclear physicist.

Over the past few decades an increasing array of molecular-level analytical probes has provided new detailed insight into mineral and radionuclide interfacial reactivity in subsurface environments. This capability has not only helped change the way mineral surface reactivity is studied but also how field-scale contaminant migration problems are addressed and ultimately resolved. Here we review relatively new interfacial reactivity paradigms and assess their implications for future research directions. Specific examples include understanding the following: the role of site-to-site electron conduction at mineral surfaces and through bulk mineral phases and the effects of local chemical environment on the stability of intermediate species in oxidation-reduction reactions and the importance of mechanistic reaction pathways for defining possible reaction products and thermodynamic driving force. The discussion also includes examples of how detailed molecular/microscopic characterization of field samples has changed the way complex contaminant migration problems are conceptualized and modelled.

Capranicaite, ideally (K,☐)(Ca,Na)Al4B4Si2O18, is a new inosilicate mineral from the Vico volcanic complex collected at Capranica, Viterbo Province, Latium, Italy. It occurs in miarolitic cavities of a feldspathoid-bearing syenite ejectum and formed by late-stage metasomatic processes related to the activity of theVico volcano.

Capranicaite occurs as thin, tabular crystals no larger than 0.1 mm. Crystals are colourless, with a white streak and a vitreous lustre; they are brittle and their Mohs hardness is certainly <6. Capranicaite is non-fluorescent with good {001} cleavage and no observable parting. The calculated density is 2.41 g/cm3. Crystals are biaxial negative, non pleochroic, with α = 1.495(1), β = 1.543(1), γ = 1.544(1), 2Vobs = 7.3(2)°, 2Vcalc = 16.0°.

Capranicaiteis monoclinic P21/n, with a = 4.8507(2), b = 16.6156(6), c = 20.5445(7) Å, β = 90.245(1)°, V = 1655.82(17) Å3, Z = 4. The strongest six X-ray diffraction lines in the simulated powder pattern are [d in Å (I) (hkl)]: 3.234 (10) (124; 044), 4.104 (9) (1̄21; 121), 3.424 (8) (006), 2.184 (4) (048; 1̄64), 2.405 (4) (160), 2.425 (3) (200). EMP-WDS analysis gives: SiO2 20.70, Al2O3 32.91, B2O3 22.90, K2O 5.36, CaO 11.04, Na2O 4.08, Cs2O 2.20, sum 99.19%; the formula, based on 18 oxygens, is: (K0.69Cs0.10)Σ0.79(Ca1.19Na0.80)Σ1.99Al3.91B3.99Si2.09O18, corresponding to the ideal formula: (K,☐)(Ca,Na)Al4B4Si2O18. The crystal structure shows three overlapping layers of polyhedra parallel to (001): (1) the A layer contains periodic single chains formed by Si2O6 units with a topology not previously observed; (2) the B layer contains isolated AlO4 tetrahedra and BO3 triangles forming a sheet of six-fold rings (3Al + 3B); (3) the C layer contains two octahedral sites: M(1) and M(2), with a mixed (Ca, Na) population. Two B layers and an intermediate A layer are vertex-connected to form a bi-dimensional B-A-B network characterized by large channels not completely populated and accommodating K and minor Cs. Along c from the origin the following layer sequence results: C-[B-A-B]-C-[B-A-B]-C.

Rinkite, ideally Na2Ca4REETi(Si2O7)2OF3, is a common mineral in alkaline and peralkaline rocks. The crystal structures of five rinkite crystals from three alkaline massifs: Ilimaussaq, Greenland; Khibiny, Kola Peninsula, Russia and Mont Saint-Hilaire, Canada, have been refined as two components related by the TWIN matrix (–1 0 0, 0 –1 0, 1 0 1) (Mo-αa radiation). The crystals, a = 7.4132-7.4414, b = 5.6595-5.6816, c = 18.8181-18.9431 Å, β = 101.353-101.424(2)°, V= 776.1-786.7 Å3, space group P21lc, Z = 2, Dcalc = 3.376—3.502 g cm–3, were analysed using an electron microprobe subsequent to collection of the X-ray intensity data. Transmission electron microscopy confirmed the presence of pseudomerohedral twinning in rinkite crystals. The crystal structure of rinkite is a framework of TS (titanium silicate) blocks. The TS block consists of HOH sheets (H-heteropolyhedral, O-octahedral). The TS block in rinkite exhibits linkage and stereochemistry typical for Group I (Ti = 1 a.p.f.u.) of Ti disilicate minerals: two H sheets connect to the O sheet such that two (Si2O7) groups link to the trans edges of a Na polyhedron of the O sheet. The crystal chemistry of rinkite and nacareniobsite-(Ce) is discussed.

Diagenetic pyrite from the Silurian continental red bed-hosted Transfiguration cupriferous deposit in the Quebec Appalachians, Gaspe Belt, Canada, contains up to ∼2% (m/m) Pb. This large Pb content in pyrite contrasts with experimental determinations that indicate solubility of <0.1% (m/m) PbS in pyrite at high temperature. The distribution of Pb in pyrite is heterogeneous, with plumbiferous domains occurring as patches and concentric growth layers alternating with Mn- and Mo-bearing zones. The plumbiferous pyrite is surrounded by As- and Cu-rich rims. This compositional heterogeneity, however, is elusive under normal backscattered-electron (BSE) imaging, but it can be recognized under high-gain BSE. Proton-induced X-ray emission (PIXE) confirms the presence of Pb. Plumbiferous pyrite with >0.1% (m/m) Pb has rarely been described; it is thus possible that plumbiferous pyrite may have been overlooked in metalliferous deposits worldwide. The plumbiferous pyrite from Transfiguration has a light S-isotope composition that is characteristic of bacterial sulphate reduction. We suggest that Pb in diagenetic pyrite indicates Pb-tolerant bacterial activity and, perhaps, constitutes a biosignature of bacterial tolerance to Pb in ancient sedimentary systems.

Allanite is a common accessory mineral in igneous rocks. Allanite becomes metamict over geological time-scales as a result of the α-decay of radioactive elements in the crystal structure. This study focuses on the recrystallization of metamict allanite from Savvushka, Russia. The structural recovery produced by annealing was investigated by X-ray powder diffraction, single-crystal synchrotron X-ray diffraction and infrared spectroscopy. A kinetic analysis is presented that shows that the recrystallization process proceeds by at least two different mechanisms.