The crystal structure of zoned philipsbornite – hidalgoite, hexagonal (rhombohedral), Rm , Z = 3: a = 7.1142(4), c = 17.0973(9) A ˚ , V = 749.4(1) Å3, from the Tsumeb mine, Namibia, has been refined to R1 = 1.68% for 301 unique reflections collected on a Bruker D8 three-circle diffractometer equipped with a rotating-anode generator, multilayer optics and an APEX-II CCD detector. Chemical analysis by electron microprobe showed zoned crystals with a rim enriched in S and Fe relative to the core. The core composition is SO3 3.31, As2O5 30.57, Al2O3 23.05, FeO 1.44, PbO 33.94, H2Ocalc 9.58, total 101.79 wt.%, corresponding to Pb0.982+(Al2.92Fe0.132+)(AsO4)[(As0.72S0.27)O3.14(OH)0.85](OH)6; and the rim composition is SO3 8.88, As2O5 22.63, Al2O3 22.90, FeO 2.57, PbO 34.91, H2Ocalc 9.27, total 101.16 wt.%, corresponding to Pb0.992+(Al2.85Fe0.232+)(AsO4)[(As0.25S0.70)O3.30(OH)0.50](OH)6. Philipsbornite – hidalgoite has the alunite-type structure, sheets of corner-sharing octahedra, decorated on top and bottom by [(As,S)O4] and (AsO3OH) tetrahedra, that are linked into a three-dimensional structure by [12]-coordinated Pb2+ cations and hydrogen bonds. A new hydrogen-bonding scheme for the D2+G33+(T5+O4)(TO3OH)(OH)6 minerals is proposed.

Ferric precipitates in the water column at the San Telmo acidic mine pit lake in the Iberian Pyrite Belt, southwest Spain, have been studied by scanning electron microscopy, energy dispersive X-ray spectrometry, X-ray diffraction, X-ray fluorescence, inductively coupled plasma mass spectrometry and other complementary techniques. These Fe(III) precipitates were recovered from sediment traps which were left at different depths (25, 35, 40 and 100 m) in the lake for several months. Seasonal variations in the water chemistry were recorded to link the mineralogical findings to vertical and temporal changes in aqueous composition. The results indicate that schwertmannite is the first Fe(III) mineral to crystallize after the oxidation of Fe(II), in agreement with previous studies. Schwertmannite is kinetically favoured in comparison to other Fe(III) minerals, and it buffers the pH at 2.6–3.0. It is metastable, and alters to a (H3O+)- and (K+)-bearing jarosite (containing 58 mol.% H3O+ and 42 mol.% K+ on average) at lower pH (e.g. at pH 2.2–2.5 in the summer season), either in the water column (during settling) and/or in the benthic sediments, in a time period of weeks to months. The extent of hydronium substitution at the alkali site in the jarosite reflects the higher activity of free aqueous protons in solution (10–2.2 to 10–3.0) in comparison to the activities of K+ (10–4.5) and Na+ (10–3.2). Microscopic examination of mixed schwertmannite–jarosite precipitates found in the water column suggest that some textural and compositional features of metastable schwertmannite (e.g. the internal 'pincushion' arrangement and incorporation of trace amounts of Mg, Al, As and Pb) are conserved in the jarosite during the early stages of the mineralogical transformation, but many of these relics are lost in the later stages of crystal growth. Despite the hydronium-rich nature of the jarosite solid solution, this material is also an important sink for K+, which decreases in concentration with decreasing pH unlike most of the other major cations in the water column (notably Na+, Mg2+, Ca2+, Al3+, Fe3+, Cu2+, Zn2+). In addition to the release of Fe3+ to the aqueous solution, the conversion of schwertmannite to (H3O+, K+)-bearing jarosite consumes protons and thus may represent an additional pH control at San Telmo and other acidic mine pit lakes of the area.

Natrotitanite, ideally (Na0.5Y0.5)Ti(SiO4)O, is a new mineral from the Verkhnee Espe rare-element deposit at the northern exo-contact of the Akjailyautas granite massif in the northern part of the Tarbagatai mountain range, Eastern Kazakhstan. Both the mineral and the name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA 2010-033). Star-shaped aggregates of small short prisms of yellow or yellowish white (Na,Y,REE)-bearing titanite rimmed by thin (∼2 μm) rims of natrotitanite are embedded in yttrium-bearing fluorite and replace narsarsukite. Associated minerals are microcline, albite, quartz, riebeckite, aegirine, biotite, astrophyllite, rutile, zircon and elpidite. Natrotitanite is milky white to yellowish grey, transparent to translucent, and has a white streak and a vitreous lustre. It shows pale orange cathodoluminescence but does not fluoresce under ultraviolet light. It shows no cleavage or parting, and is brittle; the calculated density is 3.833 g cm–3. The indices of refraction, measured with the Bloss spindle stage for the wavelength 590 nm using a gel filter, are α = 1.904, γ = 2.030, and these values are in accord with the mean refractive index, 1.988, calculated from the Gladstone-Dale relation. Natrotitanite is monoclinic, C2/c, a = 6.5691(2), b = 8.6869(3), c = 7.0924(2) Å, β = 114.1269(4)°, V = 369.4(2) Å3, Z = 4, a:b:c = 0.7562:1: 0.8164. The seven strongest lines in the X-ray powder diffraction pattern [in the order d (Å), I, (hkl)] are as follows: 2.597, 10, (130); 3.248, 8, (11); 2.994, 6, (200); 1.641, 4, (330); 4.941, 3, (110); 1.498, 3, (400); 2.273, 3, (11). Chemical analysis by electron microprobe gave Nb2O5 1.28, SiO2 27.83, TiO2 35.00, SnO2 0.57, V2O3 0.36, Fe2O3 0.23, Y2O3 7.87, Ce2O3 0.83, Sm2O3 0.26, Gd2O3 0.46, Tb2O3 0.17, Dy2O3 2.45, Ho2O3 0.16, Er2O3 2.24, Tm2O3 0.50, Yb2O3 2.53, Nd2O3 0.35, Lu2O3 0.28, MnO 0.33, CaO 8.16, Na2O 5.55, F 1.52 O ≡ F –0.64, sum 98.71 wt.%. The resulting empirical formula is (Na0.39Ca0.32Y0.15Dy0.03Yb0.03Er0.03Ce0.01Ho0.01Tm0.01Gd0.01Nd0.01)Σ1.00(Ti0.95Nb0.02Sn0.01Fe3+0.01Mn0.01V0.01)Σ1.01Si1.01O4.00(O0.83F0.17), calculated on the basis of 3 cations per formula unit. The general formula is written as (Na,Ca,Y,REE)TiSiO4(O,F), and the endmember formula is (Na0.5Y0.5)Ti(SiO4)O.

The crystal structure of a composite optically continuous crystal of natrotitanite and (Na, Y)-bearing titanite was mounted on a Bruker D8 three-circle diffractometer equipped with a rotating anode generator (MoKα radiation), a multi-layer optics incident-beam path and an APEX-II CCD detector. The crystal structure was refined in space group C2/c to a final R1 index of 1.8%. Natrotitanite is isostructural with titanite, (Na + Y + REE) replacing Ca at the Ca site in the titanite structure.

A detailed crystal-chemical study of the complex layered silicate molybdophyllite was conducted using single-crystal X-ray diffraction (XRD) methods, supplemented by powder XRD, infrared (IR) and Raman spectroscopic studies, chemical analyses by energy-dispersive spectrometry (EDS) on a scanning electron microscope (SEM), and electron probe microanalysis (EPMA). The results, based on several samples from both Långban and Harstigen, Filipstad, Sweden, show that the crystal structure of molybdophyllite has an order-disorder (OD) character. The latter is especially evident in specimens from Långban which display a complex diffraction pattern characterized by the simultaneous presence of sharp spots, diffuse reflections and continuous streaks. The sharp reflections define the unit cell of the family structure (a = 3.124, c = 41.832 Å, space group R32). Two main polytypes (maximum degree of order structures) are indicated by the OD approach: a trigonal one and a monoclinic one; the latter polytype is the most common in the samples that were studied and has space group C2, with a = 16.232(6), b = 9.373(2), c = 14.060(3) Å, b = 97.36(4)º and V = 2121.5(10) Å3.

The crystal structure determination [R1 = 0.096], together with the EPMA, IR and Raman data, reveal that molybdophyllite is built up by a regular alternation of complex layers with a composition {Mg9[Si10O28(OH)8][OPb4]2}6+ and simple layers with a composition [(CO3)3·H2O]6–, leading to the ideal crystal-chemical formula Pb8Mg9[Si10O28(OH)8|O2|(CO3)3]·H2O (Z = 2).

This contribution is mainly devoted to the results obtained for molybdophyllite sensu stricto, but new data for britvinite [i.e. 'molybdophyllite-18 Å'] are also presented and its modular relationship with molybdophyllite is discussed.

Alcaparrosaite, ideally K3Ti4+Fe3+(SO4)4O(H2O)2, is a new mineral from the Alcaparrosa mine, Cerritos Bayos, El Loa Province, Antofagasta, Chile (IMA2011-024). The mineral occurs on and intergrown with coquimbite, and is also associated with ferrinatrite, krausite, pertlikite, pyrite, tamarugite and voltaite. It is a relatively early phase which forms during the oxidation of pyritic masses under increasingly arid conditions. Alcaparrosaite crystallizes from hyperacidic solutions in a chemical environment that is consistent with its association with coquimbite. It occurs as pale yellow blades and tapering prisms up to 4 mm in length, flattened on {010} and elongated along [100]. The observed crystal forms are {010}, {110}, {1.13.0} and {021}. The mineral is transparent and has a white streak, vitreous lustre, Mohs hardness of about 4, brittle tenacity, conchoidal fracture and no cleavage. The measured and calculated densities are 2.80(3) and 2.807 g cm–3, respectively. It is optically biaxial (+) with α = 1.643(1), β = 1.655(1), γ = 1.680(1) (white light), 2Vmeas = 70(2)° and 2Vcalc = 70.3°. The mineral exhibits strong parallel dispersion, r < v. The optical orientation is X = b; Y^c = 27° in the obtuse angle β. No pleochroism was observed. Electron-microprobe analyses (average of 4) provided: Na2O 0.32, K2O 20.44, Fe2O3 11.58, TiO2 11.77, P2O50.55, SO347.52, H2O 5.79 (calc); total 97.97 wt.%. The empirical formula (based on 19 O) is (K2.89Na0.07)Σ2.96Ti0.984+Fe0.973+(S0.99P0.01O4)4O0.72(OH)0.28(H2O)2. The mineral is hydrophobic, insoluble in cold and hot water, very slowly soluble in acids and decomposes slowly in bases. Alcaparrosaite is monoclinic, C2/c, with the cell parameters a = 7.55943(14), b = 16.7923(3), c = 12.1783(9) Å, β = 94.076(7)°, V = 1542.01(12) Å3 and Z = 4. The eight strongest lines in the X-ray powder diffraction pattern [dobs in A ˚ (Irel) (hkl)] are 6.907 (41) (021,110); 3.628 (34) (023,13); 3.320 (32) (02); 3.096 (100) (202,33,150); 3.000 (40) (51); 2.704 (38) (23,152); 1.9283 (30) (55); 1.8406 (31) (53,06). In the structure of alcaparrosaite (R1 = 2.57% for 1725 Fo > 4σF), Ti4+ and Fe3+, in roughly equal amounts, occupy the same octahedrally coordinated site. Octahedra are linked into dimers by corner sharing. The SO4 tetrahedra link the dimers into chains parallel to [001] and link the chains into undulating sheets parallel to {010}. The sheets link via 10- and 11-coordinated K atoms in the interlayer region. The structure shares some features with that of goldichite.

Ianbruceite, ideally [Zn2(OH)(H2O)(AsO4)](H2O)2, is a new supergene mineral from the Tsumeb mine, Otjikoto (Oshikoto) region, Namibia. It occurs as thin platy crystals up to 80 μm long and a few μm thick, which form flattened aggregates up to 0.10 mm across, and ellipsoidal aggregates up to 0.5 mm across. It is associated with coarse white leiteite, dark blue köttigite, minor legrandite and adamite. Ianbruceite is sky blue to very pale blue with a white streak and a vitreous lustre; it does not fluoresce under ultraviolet light. It has perfect cleavage parallel to (100), is flexible, and deforms plastically. The Mohs hardness is 1 and the calculated density is 3.197 g cm-3. The refractive indices are α = 1.601, β = 1.660, γ = 1.662, all ±0.002; 2Vobs = 18(2)°, 2Vcalc = 20°, and the dispersion is r < v, weak. Ianbruceite is monoclinic, space group P21/c, a = 11.793(2), b = 9.1138(14), c = 6.8265(10) Å, β = 103.859(9)°, V = 712.3(3) Å3, Z = 4, a:b:c = 1.2940:1:0.7490. The seven strongest lines in the X-ray powder diffraction pattern [d(Å), I, (hkl)] are as follows: 11.29, 100, (100); 2.922, 17, (130); 3.143, 15, (202); 3.744, 11, (300); 2.655, 9, (230); 1.598, 8, (152); 2.252, 7, (222). Chemical analysis by electron microprobe gave As2O5 36.27, As2O3 1.26, Al2O3 0.37, ZnO 49.72, MnO 0.32, FeO 0.71, K2O 0.25, H2Ocalc 19.89, sum 108.79 wt.%; the very high oxide sum is due to the fact that the calculated H2O content is determined from crystal-structure analysis, but H2O is lost under vacuum in the electron microprobe.

The crystal structure of ianbruceite was solved by direct methods and refined to an R1 index of 8.6%. The As is tetrahedrally coordinated by four O anions with a mean As O distance of 1.687 Å. Zigzag [[5]Zn[6]Znϕ7] chains extend in the c direction and are linked in the b direction by sharing corners with (AsO4) tetrahedra to form slabs with a composition [Zn2(OH)(H2O)(AsO4)]. The space between these slabs is filled with disordered (H2O) groups and minor lone-pair stereoactive As3+. The ideal formula derived from chemical analysis and crystal-structure solution and refinement is [Zn2(OH)(H2O)(AsO4)](H2O)2.

Davidlloydite, ideally Zn3(AsO4)2(H2O)4, is a new supergene mineral from the Tsumeb mine, Otjikoto (Oshikoto) region, Namibia. It occurs as elongated prisms (∼10:1 length-to-width ratio) that are flattened on {010}, and up to 100 × 20 × 10 μm in size. The crystals occur as aggregates (up to 500 μm across) of subparallel to slightly diverging prisms lying partly on and partly embedded in fine-grained calcioandyrobertsite. Crystals are prismatic along [001] and flattened on {010}, and show the forms {010} dominant and {100} subsidiary. Davidlloydite is colourless with a white streak and a vitreous lustre; it does not fluoresce under ultraviolet light. The cleavage is distinct on {010}, and no parting or twinning was observed. The Mohs hardness is 3 – 4. Davidlloydite is brittle with an irregular to hackly fracture. The calculated density is 3.661 g cm–3. Optical properties were measured with a Bloss spindle stage for the wavelength 590 nm using a gel filter. The indices of refraction are α = 1.671, β = 1.687, γ = 1.695, all ±0.002; the calculated birefringence is 0.024; 2Vobs = 65.4(6)°, 2Vcalc = 70°; the dispersion is r < v, weak; pleochroism was not observed. Davidlloydite is triclinic, space group P1, with a = 5.9756(4), b = 7.6002(5), c = 5.4471(4) Å, α = 84.2892(9), β = 90.4920(9), γ = 87.9958(9)°, V = 245.99(5) Å3, Z = 1 and a:b:c = 0.7861:1:0.7167. The seven strongest lines in the X-ray powder diffraction pattern [listed as d (Å), I, (hkl)] are as follows: 4.620, 100, (011, 10); 7.526, 71, (010); 2.974, 49, (200, 01); 3.253, 40, (021, 120); 2.701, 39, (10, 002, 1); 5.409, 37, (001); 2.810, 37, (210). Chemical analysis by electron microprobe gave As2O5 43.03, ZnO 37.95, CuO 5.65, H2O(calc) 13.27, sum 99.90 wt.%. The H2O content and the valence state of As were determined by crystal structure analysis. On the basis of 12 anions with H2O = 4 a.p.f.u., the empirical formula is (Zn2.53Cu0.39)Σ2.92As2.03O8(H2O)4.

The crystal structure of davidlloydite was solved by direct methods and refined to an R1 index of 1.51% based on 1422 unique observed reflections collected on a three-circle rotating-anode (MoKα radiation) diffractometer equipped with multilayer optics and an APEX-II detector. In the structure of davidlloydite, sheets of corner-sharing (As5+O4) and (ZnO4) tetrahedra are linked by ZnO2(H2O)4 octahedra. The structure is related to that of parahopeite.

Melt compositions in equilibrium with peridotite assemblages were determined in the analogue system Na2O–CaO–MgO–Al2O3–SiO2–CO2 at 3 GPa with Ca/Ca + Mg = 0.56–0.43 and up to 6 wt.% Na2O. There is a greater compositional range generated isobarically over a larger temperature interval than in a sodium-absent system: increasing sodium content drives liquids to compositions with lower CaO and higher SiO2 concentrations. A positive correlation between silica and Na2O content of liquids produced at constant temperature is due to the depolymerization of silicate tetrahedra in the presence of monovalent cations, as in the volatile-free system. Liquids with Na2O >6 wt.% occur in association with wehrlites as the composition of diopsidic pyroxene expands towards enstatite with addition of Na2O, decreasing the orthopyroxene content of peridotite. The orthopyroxene-out curve intersects an enriched mantle solidus at 3 GPa where near-solidus liquids have Na2O = 7 1.5 wt.%. Sodium partitioning between a metaluminous liquid and clinopyroxene follows the jadeite partitioning models calculated for the dry silicate system but sodium partitions into peralkaline carbonated liquids as both the pyroxene and the carbonate molecules. The peralkaline liquids generated are essentially carbonated silicate melts that are analogous to silica-bearing carbonatites and silicocarbonatites from a range of possible metasomatized mantle sources.

Approaches currently used for remediating acid mine drainage (chiefly active chemical treatment and passive bioremediation systems) have a number of major detractions, including their failure to recover potentially valuable metals from these waters. Bioremediation strategies that utilize reactor-housed microorganisms can circumvent this problem, but have tended not to be widely used due to their relatively high costs. We have devised innovative approaches for remediating mine waters that use acidophilic bacteria to remove metals either as oxidized or reduced phases, using modular bioreactors that are designed to operate at minimal cost and to generate products that have commercial value. A composite system is described that combines microbial oxidation of ferrous iron with abiotic precipitation of ferric iron as schwertmannite, a mineral that has commercial value as an absorbent of arsenate and other environmental pollutants, and as a pigment. Sulfidogenic bioreactors maintained at acidic pH values are used to selectively precipitate metal sulfides, such as CuS. Tests with synthetic mine drainage containing mixtures of soluble metals confirmed that these systems can generate relatively pure mineral deposits from complex acid waters. The units are designed to be configured differently, according to the nature of the mine water requiring treatment.

In the UK, most intermediate level radioactive waste is packaged in stainless steel containers. It is important that containers should maintain their integrity for extended periods of storage prior to final disposal. A prototype 4 metre box fabricated from 304S11 stainless steel was monitored at an inland rural building for over twelve years to gain experience in monitoring environmental conditions and corrosion during storage. A wide range of different types of aerosol particles were observed on the surfaces and in the air. They contained corrosive ions such as chloride, as well as other anions such as sulfate and nitrate. The chloride deposition rate was between 0.1 and 4 μg cm−2 yr−1 depending on the orientation and location of the surface, with a chloride/sulfate ratio ranging from ∼0.3–2. The temperature and relative humidity typically ranged from 0–30°C and 40–90%, respectively. The greatest degree of corrosion developed on the base of the box, which had elevated chloride concentrations (10–140 μg cm−2). However, there was little evidence of corrosion propagation on the surface of the box and no evidence of stress corrosion cracking. The average pit propagation rates on a 316L coupon mounted next to the 4 m box were <1 μm yr−1.

The structure topology and crystal chemistry have been considered for ten astrophyllite-group minerals that contain the HOH layer, a central trioctahedral (O) sheet and two adjacent (H) sheets of [5]- and [6]-coordinated D polyhedra and the astrophyllite (T4O12) ribbons. The HOH layer is characterized by a planar cell with a ∼5.4, b ∼11.9 A ˚ and a^b ∼103°. The ideal composition of the O sheet is Fe72+ (astrophyllite) or Mn72+(kupletskite). All structures consist of an HOH layer and an I (intermediate) block that consists of atoms between two HOH layers. In the astrophyllite group, there are two types of structures based on the type of linkage of HOH layers: (1) HOH layers link directly where they share common vertices of D octahedra, and (2) HOH layers do not link directly via polyhedra of the H sheets. The type-1 structure occurs in astrophyllite, niobophyllite, nalivkinite, tarbagataite, kupletskite, niobokupletskite and kupletskite-(Cs); the type-2 structure occurs in magnesioastrophyllite, sveinbergeite and devitoite. The general formulae for the eight astrophyllite-group minerals (astrophyllite, niobophyllite, nalivkinite, tarbagataite, kupletskite, niobokupletskite, kupletskite-(Cs), magnesioastrophyllite) and for the extended astrophyllite group including devitoite and sveinbergeite are A2BC7D2T8O26(OH)4X0–1 and A2pBrC7D2(T4O12)2IXD2OXA4OXDnP, respectively, where C and D are cations of the O and H sheets, C =[6](Fe2+, Mn, Fe3+, Na, Mg, Zn) at the M(1–4) sites; D = [6,5](Ti, Nb, Zr, Fe3+); T = Si, minor Al; A2pBrI is the composition of the I block where p = 1,2; r = 1,2; A = K, Cs, Li, Ba, H2O, ☐; B = Na, Ca, Ba, H2O, ☐; I represents the composition of the central part of the I block, excluding peripheral layers of the form A2B; X = O, OH, F and H2O; n = 0, 1, 2. Two topological issues have been considered: (1) the pattern of sizes of the M octahedra in the O sheet, M(1) > M(2) > M(3) > M(4) and (2) different topologies of the HOH layer in magnesioastrophyllite and all other structures of the astrophyllite group.

This study describes geochemical barriers that have developed at three different localities in sulfiderich tailings in the Kemerovo region of Western Siberia, Russia. Iron oxyhydroxides, gypsum, malachite, chalcanthite, goslarite, bianchite, gunningite and copper and zinc chlorides crystallized in the sequence specified at an evaporative barrier around glassy slag produced by the Belovo zinc processing plant. A complex cemented barrier that has developed within the old Salair sulfide tailings contains two well defined layers: an upper layer containing Fe(III) minerals and gypsum as cements in which Pb, As, Mo, Ni and Co have been deposited; and (2) a lower calcite- and gypsum-bearing layer, in which phases containing Zn, Cd and Cu have been deposited. A complex organic-mineral barrier below the Ursk sulfide tailings consists of peaty organic matter, clay minerals and iron oxyhydroxides cemented by gypsum. Elements that have leached from the tailings are present in this barrier in a variety of different forms: Ca and Mn are present as water-soluble species; Cu, Fe and Zn are present as species produced by interaction with organic matter via ion-exchange, metal humate formation and cation bridging in organic-mineral complexes; Pb and As are co-precipitated with and/or adsorbed onto iron oxyhydroxides; gold has been deposited as minute particles of native metal. The mechanisms for the formation of the different geochemical barriers are discussed.

With potential storage of several hundred years underground in a geological disposal facility (GDF) before closure, there is a requirement for radioactive waste packages to perform adequately. Over the past 25 years, cementitous grouts based on blast furnace slag (BFS) and ordinary Portland cement (OPC), have been used in the UK to immobilize intermediate-level waste (ILW), Magnox swarf, and currently such wasteforms are in surface storage awaiting geological disposal. Magnox fuel cladding will slowly corrode when encapsulated in alkaline cementitious grouts to produce hydrogen gas and an expansive corrosion product. Expansive corrosion products may lead to degradation of the wasteform and, if extensive, could affect the container. This study investigated the acute and chronic rates of corrosion of unirradiated Magnox swarf encapsulated in a BFS/OPC grout over a range of temperatures (25, 40, 60, 75 and 90°C) for curing times of up to 2½ years. Structural product degradation starts to develop as the tensile strength of the grout is approached by the expansive forces generated. Deformation of some experimental containers was also noted. An estimate of the time taken for a grouted product to fracture from this study due to the corrosion solely of Magnox is 350 years for storage at 25°C. Although not fully described in this paper, the main cement phases were calcium silicate hydrate, portlandite and gehlenite; the main product of Magnox corrosion was brucite. The curing temperature did not affect the compositions of the Magnox metal, corrosion product or grout.

Hielscherite, ideally Ca3Si(OH)6(SO4)(SO3)·11H2O, (IMA 2011-037) is the first ettringite-group mineral with essential sulfite. We have identified a continuous natural solid-solution series from endmember thaumasite, Ca3Si(OH)6(SO4)(CO3)·12H2O, to a composition with at least 77 mol.% endmember hielscherite. In this series, the SO3:CO3 ratio is variable, whereas the SO4 content remains constant. Compositions with more than 50 mol.% endmember hielscherite have only been found at Graulay quarry near Hillesheim in the western Eifel Mountains, Rhineland-Palatinate, where they occur with phillipsite-K, chabazite-Ca and gypsum in cavities in alkaline basalt. Sulfite-rich thaumasite has been found in hydrothermal assemblages in young alkaline basalts in two volcanic regions of Germany: it is widespread at Graulay quarry and occurs at Rother Kopf, Schellkopf and Bellerberg quarries in Eifel district; it has also been found at Zeilberg quarry, Franconia, Bavaria. Hielscherite forms matted fibrous aggregates up to 1 cm across and groups of acicular to prismatic hexagonal crystals up to 0.3 × 0.3 × 1.5 mm. Individual crystals are colourless and transparent with a vitreous lustre and crystal aggregates are white with a silky lustre. The Mohs hardness is 2–2½. Measured and calculated densities are Dmeas = 1.82(3) and Dcalc = 1.79 g cm–3. Hielscherite is optically uniaxial (–), ω = 1.494(2), ε = 1.476(2). The mean chemical composition of holotype material (determined by electron microprobe for Ca, Al, Si, and S and gas chromatography for C, H and N, with the S4+:S6+ ratio from the crystal-structure data) is CaO 27.15, Al2O3 2.33, SiO2 7.04, CO2 2.71, SO2 6.40, SO3 12.91, N2O5 0.42, H2O 39.22, total 98.18 wt.%. The empirical formula on the basis of 3 Ca atoms per formula unit is Ca3(Si0.73Al0.28)Σ1.01(OH)5.71(SO4)1.00(SO3)0.62(CO3)0.38(NO3)0.05·10.63H2O. The presence of sulfite was confirmed by crystal-structure analysis and infrared and X-ray absorption near edge structure spectra. The crystal structure of sulfite-rich thaumasite from Zeilberg quarry was solved by direct methods based on single-crystal X-ray diffraction data (R1 = 0.064). The structure of hielscherite was refined using the Rietveld method (Rwp = 0.0317). Hielscherite is hexagonal, P63, a = 11.1178(2), c = 10.5381(2) Å, V = 1128.06(4) Å3 and Z = 2. The strongest reflections in the X-ray powder pattern [(d, Å (I)(hkl)] are: 9.62(100)(010,100); 5.551(50)(110); 4.616(37)(012,102); 3.823(64)(112); 3.436(25)(211), 2.742(38)(032,302), 2.528(37)(123,213), 2.180(35)(042,402;223). In both hielscherite and sulfite-rich thaumasite, pyramidal sulfite groups occupy the same site as trigonal carbonate groups, with analogous O sites, whereas tetrahedral sulfate groups occupy separate positions. Hielscherite is named in honour of the German mineral collector Klaus Hielscher (b. 1957).

Rickturnerite, which has the ideal formula Pb7O4[Mg(OH)4](OH)Cl3, is a new mineral from Torr Works (Merehead) quarry, near the village of Cranmore in Somerset, United Kingdom. It occurs as pale emerald green to grey porous aggregates of disordered interwoven minute fibrous crystals with mereheadite, cerussite, calcite, aragonite, mimetite, hydrocerussite, “plumbonacrite” and an uncharacterized lead oxychloride, in cavities inside a manganite and pyrolusite pod. The crystals are typically less than 5 μm wide and 200 μm long, but they can reach 40 × 100 μm in cross-section and over 1 mm in length. The mineral is translucent with a vitreous lustre and each needle is brittle with an indistinct cleavage, breaking with a splintery fracture. The streak is white, the Mohs hardness ∼3 and the density calculated using the empirical formula 6.886 g cm–3. Electron microprobe analyses yielded PbO 87.7, MgO 1.79, CuO 0.14, Cl 6.62 wt.%; H2O was calculated on the basis of structural considerations as 2.27 wt.% totalling 97.02 wt.%. A charge-balanced formula, based on 12 anions, is Pb7.16Mg0.81Cu0.03Cl3.40H4.60O8.60. Rickturnerite is orthorhombic Pnma, with a = 5.8024(6), b = 22.717(2), c = 25.879(3) Å, V = 3411.2(6) Å3 and Z = 8. The diffraction pattern contains strong reflections that define a subcell with a = 5.8034(5), b = 11.3574(9), c = 12.939(2) Å, V = 852.9(6) Å3 (space group Pmm2 which is related to the real unit cell by the transformation matrix [100/020/002]), and weak reflections that correspond to doubled b and c parameters. Since the difference between the large and small cells is only in a number of split and low-occupancy positions in the disordered region of the structure we provide the description of the subcell structure. The five strongest lines in the X-ray powder diffraction pattern [listed as dobs (Å), Iobs, (hkl)] are as follows: 6.474, 100, (400); 3.233, 73, (107); 2.867, 57, (705); 5.636, 44, (011); 3.112, 31, (802). The crystal structure was solved by direct methods and refined using 1318 unique reflections to R1 = 0.063. The structure is composed of a fully ordered part consisting of double [O2Pb3]2+ chains of oxocentred [OPb4] tetrahedra extended along the b-axis, which together with Cl– ions form 2-dimensional blocks parallel to (001). In between these blocks, there is a disordered region containing ordered [Mg(OH)6]4– octahedra and low-occupancy Pb and OH sites with a slight degree of ordering; these produce the weak supercell reflections.

Matulaite was first described by Moore and Ito (1980) from the Bachman mine, Hellertown, Northampton County, Pennsylvania, USA. Its ideal formula was reported as CaAl18(PO4)12(OH)20·28H2O, based on wet-chemical analysis. Re-examination of both existing cotype specimens of matulaite revealed no material matching the powder or single-crystal X-ray diffraction data reported for the species. Other samples examined from the type locality, as well as from the LCA pegmatite in North Carolina, USA, and Fumade, Tarn, France, provided material crystallographically consistent with matulaite: P21/n, a = 10.604(2), b = 16.608(4), c = 20.647(5) Å , b = 98.848(7)° and Z = 4. Electron microprobe and crystal structure analysis of newly studied material from the type locality showed the ideal formula of matulaite to be Fe3+ Al7(PO4)4(PO3OH)2(OH)8(H2O)8˙8H2O. The chemical composition reported by Moore and Ito (1980) was most probably determined on a mixture of mostly kobokoboite and afmite, with lesser amounts of crandallite. As there is no matulaite on any of the existing cotype specimens of the species, the two specimens used to obtain the new chemical analyses, powder and single-crystal X-ray diffraction data and the structure determination are designated as neotypes. The neotypes have also been used to obtain crystal morphology and new measurements of the physical and optical properties of the species. The neotypes and new data have been approved by the CNMNC, proposal 11-F. The crystal structure of matulaite contains seven-member chain segments of AlO6 octahedra decorated by PO4 tetrahedra. The PO4 tetrahedra also link to isolated FeO6 octahedra, resulting in a 'pinwheel' Fe(PO4)6 group. The linkage of octahedra and tetrahedra defines a thick layer parallel to {001}. The only linkage between layers is via hydrogen bonding to interlayer water molecules.

The island of São Vicente has the most abundant carbonatite outcrops in the Cape Verde Islands. A field survey of the main outcrops has shown that they consist of extrusive carbonatites, carbonatite dykes and small apophyses of intrusive carbonatite. These outcrops are spatially related to nephelinites. The compositions of the extrusive carbonatites and dykes plot close to, and within, the magnesiocarbonatite field. In contrast, the intrusive carbonatites are calciocarbonatites, with similar average strontium contents to those of extrusive carbonatites and dykes (around 4000 ppm), but remarkably low barium, niobium and total rare earth element concentrations. Whole-rock geochemistry indicates a strong affinity between the nephelinites and intrusive carbonatites, such that the latter could represent fractionation products of the same parental magma. This is in agreement with radiogenic isotope geochemistry, which shows a very restricted range of compositions in the Sr, Nd and Pb systems. Fractionation from a common parental magma occurred in two main steps: high-temperature nephelinite crystallization and high-temperature carbonatite immiscibility. The carbonatitic melts crystallized in two different environments, as follows: (1) a shallow intrusive environment, giving rise to the early calciocarbonatite cumulates; and (2) a vapour-dominated, extrusive environment, producing the later magnesiocarbonatites.

The capabilities of the asymmetrical flow field-flow fractionation (AsFlFFF) technique coupled with inductively coupled plasma mass spectrometry and UV–Vis spectrophotometry in the characterization of synthetic and natural colloidal samples are demonstrated in two different systems. The first system is a sol of hectorite which was co-precipitated in the presence of Lu. The results show that hectorite nanoparticles can be mobilized from a bulk sample and that they still contain the dopant Lu, which is homogeneously incorporated into the hectorite crystal structure. The second system is a natural groundwater from the Gorleben site on the northern German plain, which is being tentatively explored to assess its suitability as a nuclear waste repository. Colloidal matter heterogeneity is evident in this system. Alkaline-earth elements are mainly found as ionic species. Rare earth elements (REEs) and actinides are distributed in two main colloidal fractions: the heavier REEs and U are concentrated in the <4 nm fraction corresponding to the size range of organic colloidal particles, whereas lighter REEs and Th are concentrated in colloidal particles between 4 and 18 nm in size that are both organic and inorganic in nature. Similar results are reported for another sample from the same site, collected ∼2 km from the first one, demonstrating the homogeneity of the aquifer system and/or a possible colloid migration pathway. The extent of the reversibility of colloid–radionuclide interactions remains to be evaluated.

Two new lead oxychloride minerals, hereroite [Pb32(O, ☐)21](AsO4)2((Si,As,V,Mo)O4)2Cl10 and vladkrivovichevite [Pb32O18][Pb4Mn2O]Cl14(BO3)8·2H2O occur in association with asisite, damaraite, kombatite, sahlinite, copper, quartz, barysilite, Mn silicates and a number of Mn oxyhydroxide minerals on a specimen from the Kombat mine in Namibia. The minerals formed as late-stage products of hydrothermal reworking of primary sulfide minerals.

Hereroite is monoclinic, C2/c with a = 23.14(1), b = 22.65(1), c = 12.39(1) Å, β = 102.00(5)°, V = 6351.6(41) Å3 from powder-diffraction data and a = 23.139(4), b = 22.684(4), c = 12.389(2) Å, β = 102.090(3)°, V = 6358.8(18) Å3 from single-crystal data. It is bright orange, with white streak and adamantine lustre. It is brittle with no observed parting or cleavage and has a conchoidal fracture. The calculated density is 8.15 g cm–3. The mean refractive index in air at 589 nm is 2.38. The six strongest reflections in the X-ray powder diffraction pattern [d in Å, (I), (hkl)] are as follows: 2.982(100)(51); 2.795(47)(80); 1.986(24)(8); 1.641(24)(11..); 3.512(23)(61); 3.901(21)(511). Hereroite is named for the Herero people, one of the indigenous tribal groupings in the region where the Kombat mine is located.

Vladkrivovichevite is orthorhombic, Pmmn with a = 12.87(5), b = 27.7(4), c = 11.46(3) Å, V = 4080.1(5) Å3, from powder-diffraction data and a = 12.759(1), b = 27.169(4), c = 11.515(1) Å, V = 3992.0(9) Å3, Z = 2, from single-crystal data. It is pale greenish yellow, with white streak and adamantine lustre. It is brittle with no observed parting or cleavage and has a conchoidal fracture. The calculated density is 7.40 g cm–3. The mean refractive indices in air at 589 nm are 2.30 and 2.34. The six strongest reflections in the X-ray powder diffraction pattern [d in Å, (I), (hkl)] are as follows: 2.860(100)(370); 2.733(84)(073); 3.707(49)(073); 3.068(37)(401); 2.075(32)(473); 1.601(32)(3.14.3). Vladkrivovichevite is named in honour of Prof. Dr Vladimir Gerasimovich Krivovichev (b. 24.04.1946), Head of the Department of Mineralogy, Geological Faculty, St Petersburg State University.

The crystal structures of hereroite and vladkrivovichevite consist of alternating litharge-like O – Pb double layers and chlorine sheets and both are structurally related to other layered lead oxychlorides. In hereroite, tetrahedral AsO4 and (Si, As, V, Mo)O4 groups locate in defects within the O – Pb block, which combines square 'symesite-type' and double-square 'kombatite-type' cavities in its crystal structure. The structure of vladkrivovichevite is based on O – Pb derivative blocks with the interlayer occupied by Cl– anions and oxocentred OPb4Mn2 octahedra whose eight triangular faces are capped by triangular borate anions, BO33–.

Electron-microprobe analyses of Russian and Mongolian chevkinite-group minerals from little-known host lithologies, including various metasomatic rocks, quartzolites and an apatite deposit, are presented. The mineral species analysed include chevkinite-(Ce), perrierite-(Ce), polyakovite-(Ce) and Sr- and Zr-rich perrierite-(Ce). Compositional variation in the Sr-rich members of the group is broadly represented by the exchange vector (Fe + Mn + Al + REE) ↔ (Ca + Sr + Ti + Zr). Despite the varied parageneses, the chevkinite-(Ce) compositions are similar to previously published data. Many crystals have strong internal compositional variations, partly produced during primary crystallization and partly during low-temperature hydrothermal alteration.