The crystal structure of karibibite, Fe33+(As3+O2)4(As23+O5)(OH), from the Urucum mine (Minas Gerais, Brazil), was solved and refined from electron diffraction tomography data [R1 = 18.8% for F > 4σ(F)] and further confirmed by synchrotron X-ray diffraction and density functional theory (DFT) calculations. The mineral is orthorhombic, space group Pnma and unit-cell parameters (synchrotron X-ray diffraction) are a = 7.2558(3), b = 27.992(1), c = 6.5243 (3) Å, V = 1325.10(8) Å3, Z = 4. The crystal structure of karibibbite consists of bands of Fe3+O6 octahedra running along a framed by two chains of AsO3 trigonal pyramids at each side, and along c by As2O5 dimers above and below. Each band is composed of ribbons of three edge-sharing Fe3+O6 octahedra, apex-connected with other ribbons in order to form a kinked band running along a. The atoms As(2) and As(3), each showing trigonal pyramidal coordination by O, share the O(4) atom to form a dimer. In turn, dimers are connected by the O(3) atoms, defining a zig-zag chain of overall (As3+O2)n-n stoichiometry. Each ribbon of (Fe3+O6) octahedra is flanked on both edges by the (As3+O2)n-n chains. The simultaneous presence of arsenite chains and dimers is previously unknown in compounds with As3+. The lone-electron pairs (4s2) of the As(2) and As(3) atoms project into the interlayer located at y = 0 and y = ½, yielding probable weak interactions with the O atoms of the facing (AsO2) chain.

The DFT calculations show that the Fe atoms have maximum spin polarization, consistent with the Fe3+ state.

The new mineral hansesmarkite (IMA2015-067), Ca2Mn2Nb6O19·20H2O, was discovered at the AS Granit larvikite quarry in Tvedalen, Larvik, Vestfold, Norway. Hansesmarkite forms faintly yellow crystals up to 0.3 mm or thin coatingsin patches on gonnardite. Hansesmarkite is biaxial (+) with refractive indices (white light): α = 1.683(2), β = 1.698(2) and γ = 1.745(3); 2V(meas.) = 60.7(6)° and 2V(calc.) = 60.3°. The mineral exhibits moderate dispersion (r > v)and is pleochroic with X (almost colourless) < Y ( pale yellow) << Z (orangey yellow). The optical orientation is X ^ c = 20°, Y ^ b = 16° and Z ^ a = 5°. The empirical formula based on five electron probemicroanalyses and calculated based on Nb = 6 apfu is (Ca1.93Na0.02K0.01)∑1.96(Mn1.79Fe0.11)∑1.90Nb6O18.84·20H2O, with H2O determined from the structure solution.The mineral is triclinic, P1, with a = 9.081(4), b = 9.982(8), c = 10.60(1) Å, α = 111.07(8), β = 101.15(6), γ = 99.39(5)°, V = 850.8(13) Å3 and Z = 1. The structure was solved at 120 K because of thermalinstability of the mineral and refined to R1 = 2.50% for Fo > 4σ. The strongest reflections in the x-ray diffraction diagram are: [dobs. in Å (I)(hkl)] 9.282(36)(001), 8.610(100)(100, 011), 3.257(30)(031, 131)and 3.058(18)(130, 212). Hansesmarkite is the third naturally occurring hexaniobate in which six edge-sharing Nb-octahedra form the Lindqvist ion. These are linked via Mn-octahedra forming rods along [100] and Ca is located between the rods, creating a three dimensional structure via hydrogen bonds.

Bariopharmacoalumite, ideally Ba0.5Al4(AsO4)3(OH)4·4H2O, is a new mineral from Cap Garonne, France. It occurs in several places within the mine as colourless to pale yellow interpenetrating cubes up to 0.5 mm across. Bariopharmacoalumite is transparent to translucent, with a white streak, has an adamantine lustre and imperfect cleavage on {001}. The Vickers hardness is 234.35 and the Mohs harness is 3.5. Bariopharmacoalumite is isotropic, with n = 1.573 (upper estimate) [calculated from reflectance values at 589 nm using Fresnel Equations]. The empirical formula, based on 20 oxygen atoms, is: (Ba0.54Cu0.03K0.01)Σ0.58(Al3.99Fe0.02)Σ4.01(AsO4)3.00(OH)3.85O0.15·4H2O and the calculated density (on the basis of the empirical formula and single-crystal unit cell) is 2.580 g/cm3. The four strongest lines in the X-ray powder diffraction pattern are [dobs(Å), Iobs,(hkl)]: 7.759, 100, (001); 5.485, 27, (011); 3.878, 27, (002); 4.454, 18, (011). Bariopharmacoalumite from Cap Garonne is cubic, space group P4̄3m with a = 7.742(4) Å, V = 464.2(4) Å3 and Z = 1. The crystal structure was solved by direct methods and refined to R1 = 0.0705 for 215 reflections with I > 4σ(I) and is consistent with members of the pharmacosiderite supergroup. Data are also presented from zoned bariopharmacoalumite–bariopharmacosiderite crystals found at the Mina Grande mine, Chile.

Stream sediment geochemistry provides an innovative method of assessing the basinal history of the Caledonian slate belts. Despite glaciation, the stream sediment geochemical patterns spatially mimic the outcrop of underlying bedrock lithologies. However, erosion from rock to sediment by fluvial processes may either increase or reduce an element’s abundance depending on the nature of its mineral host. An element held in heavy, resistate minerals will be concentrated, whereas one residing in unstable ferromagnesian minerals, which readily break down to clays during weathering, may be preferentially removed. Examples are provided from the Cr-Ni-V-Mg, base metal and Rb-Sr element suites. Primary and secondary bedrock patterns are recognized in the stream sediments. Primary patterns follow the original composition of the source bedrock, with steep gradients in the element distribution coinciding with lithostratigraphical boundaries. Such patterns also reveal subtle divisions within the established geological units for which the main compositional control was the nature of the ancient sedimentary provenance. Secondary patterns reflect remobilization of elements within the bedrock and so may cut across lithostratigraphical boundaries. These patterns (or their absence) are influenced by the thermal histories of the Caledonian basins, and so are indicative of the geotectonic regime in which the sedimentary sequences were originally deposited.

Bohseite is an orthorhombic calcium beryllium aluminosilicate with variable Al content and an endmember formula Ca4Be4Si9O24(OH4), that was discovered in the Piława Górna quarry in the eastern part of the Góry Sowie Block, ∼50 km southwest of Wrocław, SW Poland. It occurs in a zoned anatectic pegmatite dyke in close association with microcline, Cs-rich beryl, phenakite, helvite, 'lepidolite', probably bertrandite and unidentified Be-containing mica as alteration products after a primary Be mineral, probably beryl. Bohseite forms fan-like or parallel aggregates (up to 0.7 cm) of white, platy crystals (up to 2 mm long) with characteristic striations. It is white with a white streak, is translucent and has a vitreous lustre; it does not fluoresce under ultraviolet light. The cleavage is perfect on {001} and fair on {010}, and neither parting nor twinning was observed. Bohseite is brittle with a splintery fracture and Mohs hardness is 5–6. The calculated density is 2.719 g cm–3. The indices of refraction are α= 1.579, β = 1.580,γ = 1.597, all ±0.002; 2Vobs = 24(3)°, 2Vcalc = 27°; the optic orientation is as follows: X ^ a = 16.1°, Y ^ b = 16.1°, Z // c Bohseite shows orthorhombic diffraction symmetry, space group Cmcm, a = 23.204(6), b = 4.9442(9), c = 19.418(6) Å, V = 2227.7(4) Å3, Z = 4. The crystal structure was refined to an R1 value of 2.17% based on single-crystal data, and the chemical composition was determined by electron-microprobe analysis. Bohseite is isostructural with bavenite. Bohseite was originally approved with an end-member composition of Ca4Be3AlSi9O25(OH)3, but subsequent discovery of compositions with Be > 3.0 apfu led to redefinition of its end-member composition, holotype sample and locality, as reported here. There is extensive solid solution in bavenite–bohseite according to the scheme O(2)OH– + T(4)Si4+ + T(3)Be2+ ↔ O(2)O2– + T(4)Al3++ T(3)Si4+, and a general formula for the bavenite–bohseite minerals may be written as Ca4BexSi9Al4–xO28–x(OH)x, where x ranges from 2–4 apfu: Ca4Be2Si9Al2O26(OH)2 (bavenite) to Ca4Be4Si9O24(OH)4 (bohseite).

This paper describes the design, testing and validation of a simple and inexpensive spectrophotometric method for total Se analysis in aqueous solution based on the azo coupling reaction of amines. In this reaction, selenite ions react with hydroxylamine hydrochloride (NH2OH.HCl), which in turn diazotizes p-Nitroaniline and is coupled with N-1-naphthyl-ethylenediamine dihydrochloride (NEDA) to form a red coloured azo compound. This azo compound has a maximum absorption peak at 545 nm, an apparent molar absorption of 2.85x104 l mol-1 cm-1 and it follows the Beer’s law in the range from 0.01 to 2.50 mg/l with R2 = 0.9998. Interferences between the azo reaction and non-targeted ions often present in environmental samples (i.e., NO3-, CO3-, Cl- or metals) were investigated and specific protocols to overcome them were implemented. The advantages of the new method for low levels of Se in aqueous solutions are its high sensitivity and reproducibility, and the fact that measurements are simple, rapid and low-cost.

Albitite, locally aegirine- and riebeckite-bearing, formed as a result of sodium metasomatism of felsic dykes and argillites along the Melones Fault Zone near Jamestown, California. Pyrite, magnetite, hematite and titanite are common in small amounts in altered dykes. The dykes were originally plagioclase-hornblende porphyritic, and had major and trace element abundances typical of calc-alkaline rocks, whereas they now have Na2O contents as high as 11.40%. Associated fracture-filling veins are dominated by albite, but locally include aegirine, analcime, paragonite, calcite and sodic scapolite. Quartz is present in most albitic rocks, but is absent in riebeckite- and aegirine-bearing samples. Albitization predated CO2 metasomatism and formation of sericite-pyrite assemblages that are typical of gold deposits of the Mother Lode Belt.

Alkaline fluids responsible for Na-metasomatism had elevated Na+/K+ and Na+/H+ relatively high fO2, and low aH4SiO4. The presence of titanite indicates fluid. The presence of titanite indicates fluid XCO2 was low, in contrast to fluids that formed later carbonate-bearing assemblages. Sodic scapolite suggests that, at least locally, the fluids attained very high salinities.

Mass balance calculations indicate that alteration involved addition of large amounts of sodium, and the removal of SiO2 and K2O. Textural preservation, combined with volume factors calculated from specific gravity and whole rock analytical data, indicate that Na-metasomatism was essentially isovolumetric.

Sodium-rich zones along the Melones Fault Zone are closely associated with fault-bounded bodies of ultramafic rock, typically altered to talc-carbonate or quartz-magnesite-Cr muscovite assemblages. Carbonatization and talc-forming reactions in the ultramafic rocks may lead to SiO2-undersaturated fluids. Expansion of the muscovite stability field in terms of Na+/K+-Na+/H+, as a result of incorporation of Cr (up to 7.7% Cr2O3) in muscovite, would result in H+- and K+-depletion as the fluid interacts with ultramafic rocks. This could lead to fluids with elevated Na+/K+ and high pH, as documented in this occurrence.

Brannerite (UTi2O6) is among the major uranium-bearing minerals found in ore deposits, however as it has been long considered as a refractory mineral for leaching it is currently disregarded in ore deposits. Brannerite is found in a variety of geological environments with the most common occurrences being hydrothermal and pegmatitic. On the basis of scanning electron microscopy observations coupled with electron probe micro-analyses and laser ablation inductively-coupled plasma mass spectrometer analyses, this study describes the morphological features and the major- and trace-element abundances of brannerite samples from five hydrothermal and five pegmatitic localities across the world. Mineral compositions are also compared with observations from transmission electron microscopy and Raman spectrometry showing that brannerite is amorphous. Significant results include the definition of substitution trends and REE patterns, which are characteristics of either an occurrence or genetic type (hydrothermal and pegmatitic). Hence, in combination, it is possible to obtain reliable constraints for establishing a geochemical classification of brannerite. Inferred fingerprints have direct implications for forensic science and the exploration industry; they also contribute to a better understanding of metallogenic processes and to optimising the extraction of uranium.

Compositional data are presented for Nb-Ba-K-V titanates from micaceous kimberlite (Star mine, S. Africa). These data significantly extend the previously known range of solid solutions in naturally occurring members of the hollandite group. Two distinct suites of crystals occur. One is a suite of primary groundmass prismatic crystals that are Ba-K-V-rich and represent solid-solutions from the priderite series towards mannardite. The second suite consists of anhedral xenocrysts that are Ba-free. In this suite relatively Nb-rich varieties (>4.0% Nb2O5) represent solid-solution towards a niobian-bearing potassian analogue of mannardite, whereas relative Nb-poor (<3.0% Nb2O5) varieties are Nb-bearing vanadian priderites. These hollandite-group minerals have compositions that differ significantly from priderites found in lamproites.

Barstowite, ideally 3PbCl2.PbCO3.H2O is a new mineral from a lead-antimony vein at the south-western end of Bounds Cliff, St Endellion, Cornwall. It occurs as very small (0.2–0.5 mm) subparallel elongate intergrown crystals which form aggregates (up to 3 mm) containing minor inclusions of galena and jamesonite. Other associated minerals are quartz, dolomite, phosgenite, cerussite, sphalerite, pyrite and chalcopyrite. Barstowite is colourless to white and is transparent with an adamantine lustre and white streak. It is brittle, has an imperfect prismatic cleavage, and an uneven fracture. Low reflecting, barstowite has a moderate bireflectance from grey to dark grey in hue and weak to moderate anisotropy. Internal reflections (colourless) are abundant. Measured reflectance values in air and oil are tabulated. Colour values relative to the CIE illuminant C for R1 and R2 in air respectively are: Y% 12.9, 13.3; λd 477, 476; Pe% 3.5, 3.7. VHN100 111 (range 108–117); calculated Mohs hardness is 3. Infrared spectra of barstowite, phosgenite and cerussite are compared.

X-ray studies show that barstowite is monoclinic with space group P21/m and a 4.218(2), b 9.180(2), c 16.673(4) Å, β 91.49(3)°. It has a cell volume of 645.38 Å3 with Z = 2. Dcalc. is 5.76 g/cm3, Dmeas. is 5.71 g/cm3. The strongest six lines of the X-ray powder pattern are [d in Å (I) (hkl)] 4.02 (10) (022); 2.296(8) (040; ; 106); 2.377(6) (007; 026); 4.16(5) (004); 2.108(4) (200); 3.79(3) (014). The name is for the late Richard William Barstow, the Cornish mineral dealer.

Högbomite is reported from two upper-amphibolite and granulite-facies, sapphirine-bearing, Al–Mg–Fe-rich and silica-poor lens-shaped layers within the Bamble Sector, south Norway. Primary assemblages, indicating peak metamorphic conditions of 773-844°C at 7 kbar (Mg–Fe exchange thermometry), are spinel–sapphirine–biotite–gedrite, spinel–corundum–sapphirine–cordierite and orthopyroxene–biotite–cordierite–plagioclase. Högbomite formed by hydrous alteration and oxidation of primary spinel and rutile and/or ilmenite according to the generalised reaction:

Suggested conditions of högbomite formation are 550–620°C and 6–7 kbar. The högbomites contain 10.2–14.7 wt.% MgO, 04).3 wt.% ZnO, 58.9–62.1 wt.% Al2O3 and 15.6-17.6 wt.% Fe as FeO. The two högbomite may belong to different polytypes, as suggested by their differing TiO2 (9.9-10.1 versus 5.7–5.8 wt. %) and calculated Fe3+ – and H2O–contents. The partitioning of Zn between spinel and högbomite is not uniform and is considered to depend upon prevailing fo2 and aH2O.

The crystal structure of byzantievite, Ba5(Ca,REE,Y)22(Ti,Nb)18(SiO4)4[(PO4),(SiO4)]4 (BO3)9O21[(OH),F]43(H2O)1.5, a new mineral from the moraine of the Dara-i-Pioz glacier, the Alai mountain ridge, Tien-Shan Mountains, northern Tajikistan, was solved by direct methods and refined to R1 = 13.14% based on 3794 observed [Fo >4σ|F|] unique reflections measured with Mo-Kα X-radiation on a Bruker P4 diffractometer equipped with a CCD detector. Byzantievite is hexagonal, space group R3, a = 9.1202(2) Å, c = 102.145(5) Å, V = 7358.0(5) Å3, Z = 3, Dcalc. = 4.151 g cm–3. The empirical formula (electron microprobe analysis) is Ba5.05[(Ca8.99Sr0.96Fe2+0.42Na0.20)Σ10.57(Ce3.46La1.54Nd1.20Pr0.30Sm0.26Dy0.41Gd0.32Th0.39U4+0.17)Σ8.05Y3.53]Σ22.15(Ti12.31Nb5.30)Σ17.61(SiO4)4.65(PO4)3.12(BO3)8.89O22.16(OH)38.21F4.89(H2O)1.5, Z = 3, calculated on the basis of 124.5 (O + F) a.p.f.u. The H2O and OH contents were calculated from structure refinement (F + OH = 43 a.p.f.u.; H2O = 1.5 a.p.f.u..), and B was determined by SIMS. The crystal structure is a framework of Ti-Ba-Ca-REE-dominant polyhedra and SiO4, PO4 and BO3 groups. In the crystal structure, there are 50 cation sites, 23 of which are fully occupied and 27 partly occupied: six of the 27 partly-occupied sites are >50% occupied, 21 <50% occupied. The crystal structure of byzantievite is an intercalation of three components, one fully ordered with 100% occupancy of cation sites, and two partly ordered with cation-site occupancies of 67% and 17% respectively. Byzantievite is the only known mineral that contains all three of the oxyanions (BO3), (SiO4) and (PO4) as essential components.

Mg-Mn amphibole (tirodite), with or without pyroxmangite in the total absence of pyroxenes and high-calcic pyroxenoids, occurs in the Mn silicate rocks of the Sausar Group, India. The rocks were metamorphosed to amphibolite facies condition (T ∼ 650°C, P ∼ 6 kbar). Tirodite-pyroxmangite pairs developed in both carbonate-free and rhodochrosite-bearing assemblages. Also tirodite coexists with either kutnahorite or manganoan calcite in the absence of pyroxmangite. Mineral reactions inferred from modal abundances and compositions of the phases indicate stabilization of the amphibole alone from a bivalent cation-bearing residual unbuffered XCO2 system with XMn < 0.3. On the other hand, tirodite-pyroxmangite pairs appeared in unbuffered low to intermediate XCO2 assemblages with XMn > 0.35. Pyroxenes and high-calcic pyroxenoids did not appear in the present situation, though they occur elsewhere in rocks with broadly similar contents of immobile components. Closely associated assemblages of diverse mineralogy suggest that the XMn and XCO2, rather than the physical conditions of metamorphism, are the decisive factors in promoting the observed phase assemblages.

Fluorapatite with monazite-(Ce) and xenotime-(Y) microinclusions occurs in the lithium–caesium–tantalum pegmatite body A of the Volta Grande mine, Minas Gerais state, Southeast Brazil. The fluorapatite displays faint zoning, detected mainly by cathodoluminescence. Electron probe and laser ablation analyses indicate that zoning in the fluorapatite corresponds to variation in Mn and rare-earth element (REE) content. Such compositional variation is attributed to partial removal of the REE from the fluorapatite structure during a dissolution–reprecipitation process, forming monazite-(Ce) and xenotime-(Y) microinclusions in the REE-depleted zones of the fluorapatite. These inclusions exhibit an inherited geochemical signature, manifested by low Th and U concentrations when compared to monazite and xenotime crystallised from melts. Rhodochrosite and calcite inclusions are also associated with monazite-(Ce) and xenotime-(Y) and are probably products of the same process, recycling Ca, Mn, and CO32− from the fluorapatite through the following reaction: [Ca(5–2a–b–½x),Naa,(Y + REE)a,Mnb][(PO4)3–x(CO3)x(F)] + Fluid[a(2Ca2+ + P5+) + (x–b)(Ca2+) + H2O)] → [Ca5(PO4)3(F,OH)] + a[(Y + REE)PO4] + b[Mn(CO3)] + (x–b)[Ca(CO3)] + Fluid a[Na+].

On the basis of new fluid-inclusion analyses, we propose that a hot (T > 204.5°C), salty (16 wt.% eq. NaCl, attributed to LiCl), hydrous fluid mediated the dissolution–reprecipitation of the fluorapatite. This fluid corresponds to similarly described Li-rich fluids which were suggested to have re-equilibrated the mineralogical assemblage at the Volta Grande mine.

Oxo-magnesio-hastingsite, ideally NaCa2(Mg2Fe3+3)(Al2Si6)O22O2, is a new anhydrous amphibole from the Deeti volcanic cone in the Gregory rift (northern Tanzania). The mineral occurs as megacrysts up to 12 cm in size in crystal-rich tuff. Oxo-magnesio-hastingsite is brown with a vitreous lustre and has a perfect {110} cleavage. The measured density is 3.19(1) g/cm3. Ferri-kaersutite is biaxial (–), α = 1.706 (2), β = 1.715(2), γ = 1.720(2) (Na light, 589 nm). 2V (calc.) = 73°. Dispersion: r > v, weak; orientation: Y = b; Z ^ c = 8°; pleochroism: strong, Z: dark brown, Y: brown, X: light brown. The average chemical formula of the mineral derived from electron microprobe analyses, Mössbauer spectroscopy and direct water determination is (Na0.67K0.33)Σ1.00(Ca1.87Na0.14Mn0.01)Σ2.02(Mg3.27Fe3+1.25Ti0.44Al0.08)Σ5.04(Al1.80Si6.20O22)(O1.40OH0.60)Σ2.00. It has monoclinic symmetry, space group C2/m and unit-cell parameters a = 9.8837(3), b = 18.0662(6), c = 5.3107(2) Å, b = 105.278(1)o, V = 914.77(5) Å3, Z = 2. The five strongest powder-diffraction lines [d in Å, (I/Io), hkl] are: 3.383 (62) (131), 2.708 (97) (151), 2.555 (100) (), 2.349 (29) () and 2.162 (36) (261). The isotopic composition of H and O, as well as the concentration of trace elements in oxo-magnesio-hastingsite suggest its formation from a melt originated from a mantle source metasomatized by slab-derived fluids.

Scattered dunite and lherzolite nodules occur in one of the youngest basanitoid lavas on Ubekendt Ejland. They have protogranular to porphyroclastic textures. The dunites are composed of olivine (Fo93.2−91.9b), enstatite (En93.4−92.8) low in Al2O3 and CaO, and Cr-spinel (61-13% Cr2O3 and 3–55% Al2O3). A solitary lherzolite module has olivine (Fo94.7–94.1), enstatite (En94.7–94.2), Cr-rich spinel, Ti-phlogopite (11% TiO2), and hyalophane. Petrographic evidence suggests that the two latter minerals have not been introduced by magmatic injection from the host in spite of the refractory nature of the coexisting phases, and metasomatic processes prior to the last deformation are therefore indicated. Partial melting of such mantle material would presumably produce small amounts of alkaline liquids even at very high temperatures. Another lherzolite nodule from a lamprophyre dyke has minerals with lower Mg/(Mg + Fe) ratios which, together with its preserved igneous textures, suggest a high-pressure precipitate. The lowest well-esablished equilibrium temperatures of 700–830°C for both dunites and lherzolites indicate a pressure regime of 12-17 kbar, according to the oceanic geotherm, whereas unrealistically high pressure (20–5 kbar) are suggested using the continental shield geotherm.

Two types of gold can be distinguished in tetrahedrite from the Veitsch magnesite deposit, Austria. Primary gold present in unfractured massive tetrahedrite, has a grain size up to 18 μm and contains, on average, Cu 8.73, Ag 7.01, Au 78.63 and Hg 2.35 (wt.%). Secondary gold is present in fractures and is directly intergrown with digenite, covellite, Cu-thiosulphate, cuprite and chrysocolla but not with malachite or azurite. The secondary gold is up to 200 µm in size with an average composition of Cu 3.06, Ag 6.82, Au 86.41 and Hg 3.51 (wt.%). It is usually closely intergrown with thiosulphates containing up to 0.21 wt.% Au. This, together with the presence of ‘dirty’ gold with cloudy thiosulphate inclusions, directly indicates the transport and deposition of Au by a thiosulphate ligand. We believe this is the first reported direct evidence of gold transport and deposition by thiosulphate complexes in a natural environment.