Two new minerals shchurovskyite, ideally K2CaCu6O2(AsO4)4, and dmisokolovite, ideally K3Cu5AlO2(AsO4)4, are found in sublimates of the Arsenatnaya fumarole at the Second scoriacone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka Peninsula, Russia. They are associated with one another and with johillerite, bradaczekite, tilasite, melanarsite, tenorite, hematite, aphthitalite, langbeinite, orthoclase, etc. Shchurovskyiteoccurs as coarse tabular or prismatic crystals up to 0.15 mm in size or anhedral grains forming parallel aggregates and crusts up to 1.5 cm × 2 cm across. Dmisokolovite forms tabular, prismatic or dipyramidal crystals up to 0.2 mm in size, commonly combined in clusters or crusts up to0.7 cm × 1.5 cm across. Both minerals are transparent with a vitreous lustre. They are brittle, with Mohs' hardness ≈3. Shchurovskyite is olive-green or olive drab. Dmisokolovite is bright emerald-green to light green. Dcalc = 4.28 (shchurovskyite) and 4.26 (dmisokolovite)g cm–3. Both are optically biaxial; shchurovskyite: (+), α = 1.795(5), β = 1.800(5), γ = 1.810(6), 2Vmeas = 70(15)°; dmisokolovite: (–), α = 1.758(7), β = 1.782(7), γ = 1.805(8), 2Vmeas = 85(5)°. The Ramanspectra are given. Chemical data (wt.%, electron-microprobe; first value is for shchurovskyite, second for dmisokolovite): Na2O 0.00, 0.83; K2O 8.85, 10.71; Rb2O 0.11, 0.00; MgO 0.00, 0.35; CaO 4.94, 0.21; CuO 43.19, 38.67; ZnO 0.42, 0.20; Al2O30.04, 4.68; Fe2O3 0.00, 0.36; P2O5 0.59, 0.78; V2O5 0.01, 0.04; As2O5 40.72, 43.01; SO3 0.35, 0.00; total 99.22, 99.84. The empirical formulae, based on 18 O a.p.f.u., are shchurovskyite: K2.05Rb0.01Ca0.96Cu5.92Zn0.06Al0.01P0.09S0.05As3.86O18;dmisokolovite: Na0.28K2.36Mg0.09Ca0.04Cu5.04Zn0.04 Al0.95Fe0.053+P0.11As3.88O18. The strongest reflections of X-ray powder patterns [d,Å(I)(hkl)]are shchurovskyite: 8.61(100)(200, 001), 5.400(32)(110), 2.974(32)(312, 510), 2.842(47)(003, 020), 2.757(63) (601, 511), 2.373(36)(512, 420) and 2.297(31)(421, 222, 313); dmisokolovite: 8.34(95)(002), 5.433(84)(110), 2.921(66)(510, 314), 2.853(58)(511, 020) and 2.733(100)(006, 512, 602). Shchurovskyiteis monoclinic, C2, a = 17.2856(9), b = 5.6705(4), c = 8.5734(6) Å, β = 92.953(6)°, V = 839.24(9) Å3 and Z = 2. Dmisokolovite is monoclinic, C2/c, a = 17.0848(12), b = 5.7188(4), c =16.5332(12) Å, β = 91.716(6)°, V = 1614.7(2) Å3 and Z = 4. Their crystal structures [single-crystal X-ray diffraction data, R = 0.0746 (shchurovskyite) and 0.1345 (dmisokolovite: model)] are closely related in the topology of the main buildingunits. They are based on a quasi-framework consisting of AsO4 tetrahedra and polyhedra centred by Cu in shchurovskyite or by Cu and Al in dmisokolovite. K and Ca are located in channels of the quasi-framework. The minerals are named in honour of outstanding Russian geologists andmineralogists Grigory Efimovich Shchurovsky (1803–1884) and Dmitry Ivanovich Sokolov (1788–1852).

Carbon-14 is an important radionuclide in the inventory of radioactive waste and is considered to be a key radionuclide in performance assessment. In Switzerland, the 14C inventory in a cement-based repository for low- and intermediate-level radioactive waste is mainly associated with activated steel (∼85%). Anaerobic corrosion of the activated steel will determine the time-dependent release of 14C-bearing compounds from the cementitious near field into the host rock. The present study was carried out to provide an overview on the current state of the art knowledge regarding the carbon speciation during the anaerobic corrosion of activated and non-activated iron/steel and to critically assess the capability of thermodynamic modelling to predict 14C speciation in anoxic alkaline conditions. Previous experimental work showed the presence of oxidized and reduced hydrocarbons during corrosion in iron-water systems in anoxic (near neutral to alkaline) conditions which appears to be inconsistent with the negative redox potential of the system. The capability of thermodynamic modelling to predict the carbon speciation in these conditions was found to be limited due to uncertainties associated with the concept of metastability in the C–H–O system.

Bulk rock geochemistry and major- and trace-element compositions of clinopyroxene have been determined for three suites of peridotitic mantle xenoliths from the North Atlantic Craton (NAC) in northern Scotland, to establish the magmatic and metasomatic history of subcontinental lithospheric mantle (SCLM) below this region. Spinel lherzolites from the southernmost locality (Streap Com'laidh) have non-NAC mantle compositions, while the two northern xenolith suites (Loch Roag and Rinibar) are derived from the thinned NAC marginal keel. Clinopyroxene compositions have characteristic trace-element signatures which show both 'primary' and 'metasomatic' origins. We use Zr and Hf abundances to identify ancient cryptic refertilization in 'primary' clinopyroxenes. We suggest that Loch Roag and Rinibar peridotite xenoliths represent an ancient Archaean-Palaeoproterozoic SCLM with original depleted cratonic signatures which were overprinted by metasomatism around the time of intrusion of the Scourie Dyke Swarm (∼2.4 Ga). This SCLM keel was preserved during Caledonian orogenesis, although some addition of material and/or metasomatism probably also occurred, as recorded by Rinibar xenoliths. Rinibar and Streap xenoliths were entrained in Permo-Carboniferous magmas and thus were isolated from the SCLM ∼200 Ma before Loch Roag xenoliths (in an Eocene dyke). Crucially, despite their geographical location, lithospheric mantle peridotite samples from Loch Roag show no evidence of recent melting or refertilization during the Palaeogene opening of the Atlantic.

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)].

Zadovite, BaCa6[(SiO4)(PO4)](PO4)2F (R3m, a = 7.0966(1) Å, c = 25.7284(3), V = 1122.13(3) Å3, Z = 3) and aradite, BaCa6[(SiO4)(VO4)] (VO4)2F (R3m, a = 7.1300(1), c = 26.2033(9) Å, V = 1153.63(6) Å3, Z = 3) are two new mineral species of a novel modular structure type related closely to the structure of nabimusaite, KCa12(SiO4)4(SO4)2O2F. Both minerals occur in paralavas enclosed in pyrometamorphic rocks of the Hatrurim Complex, Negev desert, Israel. Zadovite and aradite are colourless, transparent with a white streak, have a vitreous lustre and an uneven fracture. Both minerals are uniaxial (–) with refractive indices (589 nm) ω = 1.711(2), ε = 1.708(2) (zadovite) and ω = 1.784(3), ε = 1.780(3) (aradite). The zadovite structure type comprises two tetrahedral sites, which may host a broad compositional range of atoms such as Si, P, V and S. Results of electron microprobe analyses show a correlation between excess Si4+ and S6+ contents, suggesting the substitution scheme 2(P,V)5+ = Si4+ + S6+ at the tetrahedral sites. This points to the possibility of new minerals isostructural with zadovite with end-member formulae BaCa6(SiO4)2[(PO4)(SO4)]F, BaCa6(SiO4)2[(VO4)(SO4)]F, BaCa6[(SiO4)1.5(SO4)0.5](PO4)2F and BaCa6[(SiO4)1.5(SO4)0.5](VO4)2F. The Raman spectra of aradite and zadovite reflect the varying PO4 (e.g. change of band intensity at ∼1031 cm–1) and VO4 contents (e.g. change of band intensity at ∼835 cm–1). The presence of SO4 leads to an additional Raman band at ∼997 cm–1. The structure of zadovite-series minerals belonging to the nabimusaite group is characterized by a 1:1 alternation of antiperovskite-like {[FCa6](TO4)2}4+ modules and Ba(TO4)2–4 modules.

A multi-methodological study of the (K,Ca)-variety of the zeolite merlinoite from Fosso Attici, Sacrofano, Italy was carried out on the basis of electron microprobe analysis in wavelength dispersive mode, singlecrystal X-ray diffraction (at 100 K), Raman and infrared spectroscopy. Thechemical formula of the merlinoite from Fosso Attici is (Na0.37K5.69)Σ=6.06(Mg0.01Ca1.93Ba0.40)Σ=2.34(Fe0.023+Al10.55Si21.38)Σ=31.9O64·19.6H2O,compatible with the ideal chemical formula K6Ca2[Al10Si22O64]·20H2O.

Anisotropic structure refinements confirmed the symmetry and the framework model previously reported (space group Immm, a = 14.066(5),b = 14.111(5), c = 9.943(3) Å at 100 K). Refinement converged with four cationic sites and six H2O sites; refined bond distances of the framework tetrahedra suggest a highly disordered Si/Al-distribution. The Raman spectrum of merlinoite (collected between 100and 4000 cm–1) is dominated by a doublet of bands between 496–422 cm–1, assigned to tetrahedral T–O–T symmetric bending modes. T–O–T antisymmetric stretching is also observed; stretching and bending modes of the H2Omolecules are only clearly visible when using a blue laser. The single-crystal near-infrared spectrum shows a very weak band at 6823 cm–1, assigned to the first overtone of the O–H stretching mode, and a band at 5209 cm–1, due to the combination of H2Ostretching and bending modes. Avery broad and convoluted absorption, extending from 3700 to 3000 cm–1 occurs in the H2O stretching region, while the ν2 bending mode of H2O is found at 1649 cm–1. The powder mid-infraredspectrum of merlinoite between 400–1300 cm–1 is dominated by tetrahedral T–O–T symmetric and antisymmetric stretches. Raman and Fourier-transform infrared spectroscopy spectra of merlinoite and phillipsite provide a quick identification tool for these zeolites,which are often confused due to their close similarity.

Gem minerals at Lava Plains, northeast Queensland, offer further insights into mantle-crustal gemformation under young basalt fields. Combined mineralogy, U-Pb age determination, oxygen isotope and petrological data on megacrysts and meta-aluminosilicate xenoliths establish a geochemical evolution in sapphire, zircon formation between 5 to 2 Ma. Sapphire megacrysts with magmatic signatures (Fe/Mg ∼100–1000, Ga/Mg 3–18) grew with ∼3 Ma micro-zircons of both mantle (δ18O 4.5–5.6%) and crustal (δ18O 9.5–10.1‰) affinities. Zircon megacrysts (3±1 Ma) show mantle and crustal characteristics, but most grew at crustal temperatures (600–800°C). Xenolith studies suggest hydrous silicate melts and fluids initiated from amphibolized mantle infiltrated into kyanite+sapphire granulitic crust (800°C, 0.7 GPa). This metasomatized the sapphire (Fe/Mg ∼50–120, Ga/Mg ∼3–11), left relict metastable sillimanite-corundum-quartz and produced minerals enriched in high field strength, large ion lithophile and rare earth elements. The gem suite suggests a syenitic parentage before its basaltic transport. Geographical trace-element typing of the sapphire megacrysts against other eastern Australian sapphires suggests a phonolitic involvement.

When crustal abundance (A, measured in atomic parts per million) of a chemical element is plotted vs. number of mineral species in which that element is an essential constituent (S), a significantly positive correlation is obtained, but with considerable scatter. Repeated exclusion of outliers at the 90% confidence level and re-fitting leads, after the sixth iteration, to a steady state in which 40 of the 70 elements initially considered define a trend with log S = 1.828 + 0.255 log a (r = 0.96), significantly steeper than the original. Three other methods for reducing the effect of outliers independently reproduce this steeper trend. The 'diversity index' D of an element is defined as the ratio of observed mineral species to those predicted from this trend. D separates elements into three groups. More than half of the elements (40 of 70) have D = 0.5–2.0. Apart from these 'typical' elements, a group of 15 elements (Sc, Cr, Ga, Br, Rb, In, Cs, La, Nd, Sm, Gd, Yb, Hf, Re and Th) form few species of their own due to being dispersed as minor solid solution constituents, and a hitherto unrecognized group of 15 elements are essential components in unusually large numbers of minerals. The anomalously diverse group consists of H, S, Cu, As, Se, Pd, Ag, Sb, Te, Pt, Au, Hg, Pb, Bi and U, with Te and Bi by far the most mineralogically diverse elements (D = 22 and 19, respectively). Possible causes and inhibitors of diversity are discussed, with reference to atomic size, electronegativity and Pearson softness, and particularly outer electronic configurations that result in distinctive stereochemistry. The principal factors encouraging mineral diversity are: (1) Particular outer electronic configurations that lead to a preference for unique coordination geometries, enhancing an element's ability to form distinctive chemical compounds and decreasing its ability to participate in solid solutions. This is particularly noteworthy for elements possessing geometrically flexible 'lone-pair cations' with an s2 outer electronic configuration. (2) Siderophilic or chalcophilic geochemical behaviour and intermediate electronegativity, allowing elements to form minerals that are not oxycompounds or halides. (3) Access to a wide range of oxidation states. The most diverse elements can occur as anions, native elements and in more than one cationic valence state.

The Mesoproterozoic Gardar Province in South Greenland developed in a continental rift-related environment. Several alkaline intrusions and associated dyke swarms were emplaced in Archaean and Ketilidian basement rocks during two main magmatic periods at 1300–1250 Ma and 1180–1140 Ma. The present investigation focuses on mafic dykes from the early magmatic period ('Older Gardar') and the identification of their possible mantle sources.

The rocks are typically fine- to coarse-grained dolerites, transitional between tholeiitic and alkaline compositions with a general predominance of Na over K. They crystallized from relatively evolved, mantle-derived melts and commonly show minor degrees of crustal contamination. Selective enrichment of the large ion lithophile elements Cs, Ba and K and the light rare-earth elements when compared to high field-strength elements indicate significant involvement of a sub-continental lithospheric mantle (SCLM) component in the generation of the magmas. This component was affected by fluid-dominated supra-subduction zone metasomatism, possibly related to the Ketilidian orogeny ∼500 Ma years prior to the onset of Gardar magmatism. Melt generation in the SCLM is further documented by the inferential presence of amphibole in the source region, negative calculated εNd(i) values (–0.47 to –4.40) and slightly elevated 87Sr/86Sr(i) (0.702987 to 0.706472) ratios when compared to bulk silicate earth as well as relatively flat heavy rare-earth element (HREE) patterns ((Gd/Yb)N = 1.4 –1.9) indicating melt generation above the garnet stability field.

The dyke rocks investigated show strong geochemical and geochronological similarities to penecontemporaneous mafic dyke swarms in North America and Central Scandinavia and a petrogenetic link is hypothesized. Considering recent plate reconstructions, it is further suggested that magmatism was formed behind a long-lived orogenic belt in response to back-arc basin formation in the time interval between 1290–1235 Ma.

The new mineral species ralphcannonite, AgZn2TlAs2S6, was discovered in the Lengenbach quarry, Binn Valley, Wallis, Switzerland. It occurs as metallic black equant, isometric to prismatic crystals, up to 50 μm, associated with dufrénoysite, hatchite, realgar and baryte. Minimum and maximum reflectance data for COM wavelengths in air are [λ (nm): R (%)]: 471.1: 25.8/27.1; 548.3: 25.2/26.6; 586.6: 24.6/25.8; 652.3: 23.9/24.8. Electron microprobe analyses give (wt.%): Cu 2.01(6), Ag 8.50(16), Zn 10.94(20), Fe 3.25(8), Hg 7.92(12), Tl 24.58(26), As 18.36(19), Sb 0.17(4), S 24.03(21), total 99.76(71). On the basis of 12 atoms per formula unit, the chemical formula of ralphcannonite is Ag0.63(2)Cu0.25(2)Zn1.35(5)Fe0.47(1)Hg0.32(2)Tl0.97(3)[As1.97(6)Sb0.01(1)]Σ1.98(5)S6.03(8). The new mineral is tetragonal, space group I42m, with a = 9.861 (2), c = 11.125(3) Å, V = 1081.8(4) Å3, Z = 4. The main diffraction lines of the calculated powder diagram are [d (in Å), intensity, hkl]: 4.100, 85, 211; 3.471, 40, 103; 2.954, 100, 222; 2.465, 24, 400; 2.460, 39, 303. The crystal structure of ralphcannonite has been refined by X-ray single-crystal data to a final R1 = 0.030, on the basis of 140 observed reflections [Fo > 4σ(Fo)]. It shows a three dimensional framework of (Ag,Zn)-centred tetrahedra (1 M1 + 2 M2), with channels parallel to [001] hosting TlS6 and (As,Sb)S3 disymmetric polyhedra. Ralphcannonite is derived from its isotype routhierite M1CuM2Hg2TlAs2S6 through the double heterovalent substitution M1Cu+ + M2Hg2+ → M1Zn2+ + M2Ag+. This substitution obeys a steric constraint, with Ag+, the largest cation relative to Zn2+ and Cu+, entering the largest M2 site, as observed in arsiccioite. The ideal crystal-chemical formula of ralphcannonite is M1ZnM2(Zn0.5Ag0.5)2TlAs2S6.

A new silicate, colinowensite, BaCuSi2O6, has been found in the Wessels mine, Kalahari Manganese Field, South Africa. It is associated with effenbergerite, wesselsite, lavinskyite, scottyite, diegogattaite, as well as with pectolite, quartz, aegirine, richterite, minerals of the garnet group and a number of different manganese and iron oxides, especially hausmannite and hematite. The mineral was named for the mineral collector and finder of the new species, Colin R. Owens, of Somerset West, South Africa. Colinowensite is brittle, with uneven fracture, and the estimated Mohs hardness is ∼4. It occurs as subhedral crystals <100 μm in size. The forms {100} and {110} are observed while {001} is always present in cleavage plates. The calculated density is 4.236 g cm–3. It is the natural analogue of the synthetic pigmentreferred to as Chinese or Han purple, which is found on artifacts from ancient and imperial China. The mineral is of dark blue to purple colour, with a purple streak, and is uniaxial (–), with ω = 1.740 (20), ε = 1.735 (20) (420 nm) and ω = 1.745 (20), ε = 1.730(20) (650 nm). The lustre is vitreous and no fluorescence is observed under either shortwave or longwave ultraviolet radiation. Avery strong pleochroism occurs from purple along the c axis to blue in a perpendicular direction. Colinowensite is not soluble in acids except HF. Electron microprobe analyses gave an average composition (wt.%) of CuO 22.53, BaO 43.43 and SiO2 34.04 yielding the empirical formula (based on 6 O a.p.f.u.) BaCuSi2O6. The new mineral is tetragonal, space group I41/acd with Z = 16, anda = 9.967(1), c = 22.290 (2) Å. Colinowensite is a cyclosilicate with [Si4O12]8– 4-membered single rings, arranged in sheets parallel to (001). The structure is further characterized by CuO4 squares sharing corners with four neighbouring silicate rings within a sheet. Ba2+ cations are bonded to ten O atoms in irregular coordination. Average Si–O, Cu–O and Ba–O bond lengths are 1.619, 1.934 and 2.943 Å, respectively. Colinowensite belongs to subdivision 9. CE of the Strunz Mineralogical Tables. In addition, based on single-crystal X-ray work, new structural data for wesselsite of chemical composition Sr0.9Ba0.1CuSi4O10 are provided.

Flamite (Ca,Na,K)2(Si,P)O4 (P63; a = 43.3726(18), c = 6.8270(4) Å; V = 11122.2(9) Å3), a natural analogue of the P,Na,K-doped high-temperature α-Ca2SiO4 modification, is a new mineral from Ca- and Al-rich paralava, an ultrahigh-temperature combustion metamorphic melt rock. The type locality is situated in the southern Hatrurim Basin, the Negev Desert, Israel. Flamite occurs as regular lamellar intergrowths with partially hydrated larnite, together with rock-forming gehlenite, rankinite and Ti-rich andradite, minor ferrian perovskite, magnesioferrite, hematite, and retrograde ettringite and calcium silicate hydrates. The mineral is greyish to yellowish, transparent with a vitreous lustre, non-fluorescent under ultraviolet light and shows no parting or cleavage; Mohs hardness is 5–5½; calculated density is 3.264 g cm–3. The empirical formula of holotype flamite (mean of 21 analyses) is (Ca1.82Na0.09K0.06(Mg,Fe,Sr,Ba)0.02)Σ1.99(Si0.82P0.18)Σ1.00O4. The strongest lines in the powder X-ray diffraction pattern are [d, Å (Iobs)]: 2.713(100), 2.765(44), 2.759(42), 1.762(32), 2.518(29), 2.402(23), 2.897(19), 1.967(18), 2.220(15), 1.813(15). The strongest bands in the Raman spectrum are 170, 260, 520, 538, 850, 863, 885, 952 and 1003 cm–1.

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).

Neptunium-237 will be present in radioactive wastes over extended time periods due to its long half-life (2.13 × 106 years). Understanding its behaviour under conditions relevant to radioactive waste disposal is therefore of particular importance. Here, microcosm experiments were established using sediments from a legacy lime workings with high-pH conditions as an analogue of cementitious intermediate-level radioactive waste disposal. To probe the influence of Fe biogeochemistry on Np(V) in these systems, additional Fe(III) (as ferrihydrite) was added to select experiments. Biogeochemical changes were tracked in experiments with low levels of Np(V) (20 Bq ml–1; 3.3 μM), whilst parallel higher concentration systems (2.5 KBq ml–1; 414 μM) allowed X-ray absorption spectroscopy. As expected, microbial reduction processes developed in microbially-active systems with an initial pH of 10; however, during microbial incubations the pH dropped from 10 to ∼7, reflecting the high levels of microbial metabolism occurring in these systems. In microbially-active systems without added Fe(III), 90% sorption of Np(V) occurred within one hour with essentially complete removal by one day. In the ferrihydrite-amended systems, complete sorption of Np(V) to ferrihydrite occurred within one hour. For higher-activity sediments, X-ray absorption spectroscopy (XAS) at end points where Fe(II) ingrowth was observed confirmed that complete reductive precipitation of Np(V) to Np(IV) had occurred under similar conditions to low-level Np experiments. Finally, pre-reduced, Fe(III)-reducing sediments, with and without added Fe(III) and held at pH 10, were spiked with Np(V). These alkaline pre-reduced sediments showed significant removal of Np to sediments, and XAS confirmed partial reduction to Np(IV) with the no Fe system, and essentially complete reduction to Np(IV) in the Fe(III)-enriched systems. This suggested an indirect, Fe(II)-mediated pathway for Np(V) reduction under alkaline conditions. Microbial analyses using 16S rRNA gene pyrosequencing suggested a role for alkali-tolerant, Gram-positive Firmicutes in coupled Fe(III) reduction and Np immobilization in these experiments.

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).

We have characterized the crystal structure of natural kutinaite, a rare mineral from the ores of Černý Důl, Czech Republic, by single-crystal X-ray diffraction and chemical analysis. We found that the structure of natural kutinaite is not identical to that of synthetic Cu14Ag6As7, previously reported to be cubic, space group Pm3m. Although topologically similar, the structure of natural kutinaite is indeed tetragonal, space group P4/mmm, with cell parameters: a = 11.789(2), c = 11.766(2) Å, V = 1635.5(4) Å3 and Z = 4. Electron microprobe analyses pointed to the (K,Tl)0.25Cu14Ag6As6.75 stoichiometry (Z = 4), or (K, Tl)Cu56Ag24As27 with Z = 16. The crystal structure of an untwinned crystal has been refined to R1 = 2.61%. It consists of clusters of eight edge-sharing tetrahedra of Cu, which alternate in a 3D chess-board manner with octahedral clusters of six Ag atoms. The latter are surrounded by triangularly coordinated copper in eight faces of a cuboctahedron. The last structure components are large cavities containing partly occupied (K,Tl) sites, coordinated by 18 Ag and As ligands. The structure is full of direct metal-metal contacts although As plays the role of anion, associating especially with copper.

The first-principles plane-wave pseudopotential method is used to study the electronic and chemical structures of pyrite (FeS2) and arsenopyrite (FeAsS). The results indicate that an antibonding interaction occurs between Fe and As atoms in arsenopyrite. This interaction results in the Fe atom being repelled towards the S atom to stabilize antibonding orbitals, causing a larger S–Fe–S angle in arsenopyrite than in pyrite and a distortion in the arsenopyrite structure. In arsenopyrite, Fe–Fe distances are alternately long and short. The low spin density of the Fe d electrons supports this configuration in arsenopyrite. However, electron density calculations indicate that there is negligible electron density present between Fe atoms. This result indicates that cation-anion interactions are dominant in arsenopyrite. The pyrite Fe 3d orbital is split below the Fermi level, whereas the arsenopyrite Fe 3d orbital is not split, which can be attributed to the stronger interatomic bonding effects between Fe and S atoms in pyrite compared to arsenopyrite. It is found that the d-p orbital interactions between Fe and S atoms lead to bonding-antibonding splitting in both pyrite and arsenopyrite. However, the bonding effects between pyrite Fe and S atoms are stronger than in arsenopyrite. In arsenopyrite, the bonding interaction between the As 4p and Fe 3d orbitals is very weak, while the antibonding effect is very strong. The p-p orbital interaction is the dominant effect in As–S bonding. Frontier orbital calculations indicate that the Fermi levels of pyrite and arsenopyrite are notably close to each other, resulting in similar electrochemical activities. Orbital coefficient results show that the pyrite Fe 3d and S 3p orbitals are the active orbitals in the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), respectively. In the case of arsenopyrite, Fe 3d orbitals are very active in both the HOMO and LUMO. Moreover, the activity of the As 4p in the HOMO is greater than S 3p, whereas the opposite situation occurs in the LUMO. Based on these results, As atoms could be one of the active sites for the oxidation of arsenopyrite. In addition, separation of arsenopyrite and pyrite could be achieved by utilizing the difference in chemical reactivities of iron in the two minerals.

Radial diffusion experiments have been carried out to assess the migration of 36Cl, as chloride, through a cementitious backfill material. Further experiments in the presence of cellulose degradation products were performed to assess the effect of organic ligands on the extent and rate of chloride diffusion. Results show that breakthrough of 36Cl is dependent on chloride concentration: as the carrier concentration increases, both breakthrough time and the quantity retained by the cement matrix decreases. Experiments in the presence of cellulose degradation products also show a decrease in time to initial breakthrough. However, uptake at various carrier concentrations in the presence of organic ligands converges at 45% of the initial concentration as equilibrium is reached. The results are consistent with organic ligands blocking sites on the cement that would otherwise be available for chloride binding, though further work is required to confirm that this is the case. Post-experimental digital autoradiographs of the cement cylinders, and elemental mapping showed evidence of increased 36Cl activity associated with black ash-like particles in the matrix, believed to correspond to partially hydrated glassy calcium-silicate-sulfate-rich clinker.