Native tungsten (IMA2011-004), W, is officially described as a new mineral from gold placers in the Bol'shaya Pol'ya river valley, Prepolar Urals, Russia, associated with yttriaite-(Y) and from quartz veins in the Mt Neroyka rock-crystal field, Ust–Puiva, Tyumenskaya Oblast', Russia. Tungsten forms polycrystalline grains and masses, and rarely cubo-octahedra. It is silver white to steel grey in colour, with metallic lustre and grey streak. The calculated density is 19.226 g/cm3. The Vickers hardness (VHN25) is 571.45 kg/mm2. In plane polarised light, tungsten is white with a pale-yellow tint and optically isotropic. Electron microprobe analyses of Bol'shaya Pol'ya river valley material provided W 99.27, Mo 0.06, Mn 0.04, Fe 0.01, total 99.38 wt.%. The five strongest powder X-ray diffraction lines are [dobs Å(I)(hkl)]: 2.2422(100)(110), 1.5835(25)(200), 1.2929(48)(211), 1.0010(23)(310) and 0.8457(24)(321). Tungsten is cubic, Im$\bar{3}$m, a = 3.1648(4) Å, V = 31.69(4) Å3 and Z = 2. Some additional occurrences of native tungsten and technogenic tungsten found in Nature are also described.

The type specimen of liskeardite, (Al, Fe)3AsO4(OH)6·5H2O, from the Marke Valley Mine, Liskeard District, Cornwall, has been reinvestigated. The revised composition from electron microprobe analyses and structure refinement is [Al29.2Fe2.8(AsO4)18(OH)42(H2O)22]·52H2O. The crystal structure was determined using synchrotron data collected on a 2 μm diameter fibre at 100 K. Liskeardite has monoclinic symmetry, space group I2, with the unit-cell parameters a = 24.576(5), b = 7.754(2) Å, c = 24.641(5) Å, and β = 90.19(1)º. The structure was refined to R = 0.059 for 9769 reflections with I > 3σ(I). It is of an open framework type in which intersecting polyhedral slabs parallel to (101) and (10) form 17.4 Å × 17.4 Å channels along [010], with water molecules occupying the channels. Small amounts (<1 wt.%) of Na, K and Cu are probably adsorbed at the channel walls The framework comprises columns of pharmacoalumite-type, intergrown with chiral chains of six cis edge-shared octahedra. It can be described in terms of cubic close packing, with vacancies at both the anion and cation sites. The compositional and structural relationships between liskeardite and pharmacoalumite are discussed and a possible mechanism for liskeardite formation is presented.

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.

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.

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.

Diegogattaite (IMA2012-096), Na2CaCu2Si8O20·H2O, is a new mineral from the Wessels mine in the Kalahari manganese fields of South Africa. It occurs as a minor phase with other copper-bearing silicates, Cu-rich pectolite, sugilite, quartz, aegirine and undifferentiated Fe-Mn oxides. Diegogattaite is pale turquoise through teal blue. It is found as sub-mm sized grains in a main crystalline patch 3–4 mm in size, and is currently known from only one sample. The mineral is transparent with a vitreous lustre and may have a good cleavage on {001}. It is brittle, with an uneven fracture and a very pale-blue streak. It is non-fluorescent in short- and long-wave UV light and has an estimated Mohs hardness of ∼5–6. Diegogattaite is biaxial (–), α = 1.598(2), β = 1.627(2), γ = 1.632(2); 2Vmeas = 44.0(6)°, 2Vcalc = 44.5°; dispersion: strong r < v, orientation: X = b, Y ≈ ⊥(001), Z ≈ a; pleochroism X colourless << Y ≈ Z blue green. The calculated density is 3.10 g/cm3. Electron-microprobe analysis gave: Na2O 8.07, CaO 7.3, CuO 20.5, FeO 0.36, SiO262.4, H2O(calc) 2.34, total 100.97 wt.%. A charge-balanced formula on the basis of 21 oxygen a.p.f.u. is: Na2.00Ca1.00Cu1.98Fe0.04Si7.99H2O21. Diegogattaite is monoclinic, space group C2/m, a = 12.2439(6) Å, b = 15.7514(4) Å, c = 10.6008(3) Å, β = 125.623(2)°, V = 1661.87(10) Å3 and Z = 4. The five strongest lines in the X-ray powder pattern are [dobs in Å (Iobs)(hkl)]: 4.25(75)(002,22,220), 3.951(77)(040), 3.261(100)(31,13), 2.898(89)(042,03,003), 2.332(66)(331,43,62,260,043). The crystal structure of diegogattaite was determined by single-crystal X-ray diffraction to final agreement indices of R1 = 0.027, wR2 = 0.071 and GoF = 1.090. It represents a completely new silicate topology based upon a double-sheet of SiO4 tetrahedra composed of connected 6482 cages. The structure of diegogattaite is related to those of synthetic nanoporous Na-Cu-Si-O-(OH)-H2O (CuSH) compounds, which are of interest to the solid-state chemistry community as potential ion-exchangers, catalysts and molecular sieves. The structure of diegogattaite forms a bridge between these structures and those of the gillespite-group minerals, including wesselsite. The close spatial association of wesselsite and diegogattaite suggests a possible reaction between them that may point to a synthetic route for the production of novel alkaline-earth-based nanoporous copper silicates.

The crystal structure of mereheadite (monoclinic, Cm, a = 17.372(1), b = 27.9419(19), c = 10.6661(6) Å, β = 93.152(5)°, V = 5169.6(5) Å3) has been solved by direct methods and refined to R1 = 0.058 for 6279 unique observed reflections. The structure consists of alternating Pb–O/OH blocks and Pb–Cl sheets oriented parallel toth e (201) plane and belongs toth e 1:1 type of lead oxide halides with PbO blocks. It contains 30 symmetrically independent Pb positions, 28 of which belong to the PbO blocks, whilst two positions (Pb12 and Pb16) are located within the tetragonal sheets of the Cl– anions. Mereheadite is thus the first naturally occurring lead oxychloride mineral with inter-layer Pb ions. The coordination configurations of the Pb atoms of the PbO blocks are distorted versions of the square antiprism. In one half of the coordination hemisphere, they are coordinated by hard O2– and OH– anions whose number varies from three to four, whereas the other coordination hemisphere invariably consists of four soft Cl– anions located at the vertices of a distorted square. The Pb12 and Pb16 atoms in between the PbO blocks have an almost planar square coordination of four Cl– anions. These PbCl4 squares are complemented by triangular TO3 groups (T = B, C) so that a sevenfold coordination is achieved. The Pb–O/OH block in mereheadite can be obtained from the ideal PbO block by the following list of procedures: (1) removal of some PbO4 groups that results in the formation of square-shaped vacancies; (2) insertion of TO3 groups into these vacancies; (3) removal of some Pb atoms (that correspond to the Pb1A and Pb2A sites), thus transforming coordination of associated O sites from tetrahedral OPb4 tot riangular OHPb3; and (4) replacement of two O2– anions by one OH– anion with twofold coordination; this results in formation of the 1×2 elongated rectangular vacancy. The structural formula that can be derived on the basis of the results of single-crystal structure determination is Pb47O24(OH)13Cl25(BO3)2(CO3). Welch et al. (1998) proposed the formula Pb2O(OH)Cl for mereheadite, which assumes that neither borate nor carbonate is an essential constituent of mereheadite and their presence in the mineral is due to disordered replacements of Cl– anions. However, our study demonstrates that this is not the case, as BO3 and CO3 groups have well-defined structural positions confined in the vacancies of the Pb–O/OH blocks and are therefore essential constituents. Our results also show that mereheadite is not a polymorph of blixite, but is in fact related to symesite. Symesite thus becomes the baseline member of a group of structurallyrelated minerals.

Mavlyanovite, ideally Mn5Si3, is a new mineral from a lamproite diatreme close to the upper reaches of the Koshmansay river, Chatkal ridge, Uzbekistan. It occurs together with unnamed manganese siliciphosphide and manganese silicicarbide minerals in round to ovoid segregations, up to 10 cm in diameter, in volcanic glass. Segregations of hexagonal prismatic mavlyanovite up to 1–2 mm occur in interstices in the matrix and tiny inclusions (1–2 μm) of alabandite and khamrabaevite occur within mavlyanovite. It is opaque with a metallic lustre, has a dark-grey streak, is brittle with a conchoidal fracture and a near-perfect basal cleavage. VHN100 is 1029–1098 kg/mm2 (Mohs hardness ~7). In plane-polarized reflected light, mavlyanovite is a pale-brownish-grey against the accompanying unnamed manganese silicicarbide (white). Reflectance values and colour data are tabulated. Average results of 19 electronmicroprobe analyses give Mn70.84, Fe 6.12, Si 22.57, Ti 0.15, P 0.18, total 99.86 wt.% leading to an empirical formula of (Mn4.66Fe0.40)5.06(Si2.91Ti0.01P0.02)2.94 based on8 a.p.f.u. The calculated density is 6.06 g/cm3, (on the basis of the empirical formula and unit-cell parameters from the structure determination). Mavlyanovite is hexagonal (P63/mcm) with a 6.8971(7), c 4.8075(4) Å, V 198.05(3) Å3 and Z = 2. The structure has been determined and refined to R1 = 0.017, wR2 = 0.044, GoF = 1.16. Mavlyanovite is the naturally-occurring analogue of synthetic Mn5Si3 which is the parent aristotype structure of the Nowotny intermetallic phases studied extensively by the material-science community. It is also the Mn-dominant analogue of xifengite Fe5Si3. The mineral name honours Academician Gani Arifkhanovich Mavlyanov (1910–1988), for his contributions to the understanding of the geology of Uzbekistan.

Type specimens of the molybdoarsenates betpakdalite, natrobetpakdalite and obradovicite and the molybdophosphates mendozavilite, paramendozavilite and melkovite, and similar material from other sources, have been examined in an effort to elucidate the relations among these phases, which we designate as the heteropolymolybdate family of minerals. Using electron microprobe analysis, X-ray powder diffraction and single-crystal X-ray diffraction with crystal structure determination where possible, it was found that natrobetpakdalite, mendozavilite and melkovite are isostructural with betpakdalite and that obradovicite has a closely related structure.

The betpakdalite and obradovicite structure types are based on frameworks containing four-member clusters of edge-sharing MoO6 octahedra that link by sharing corners with other clusters, with Fe3+O6 octahedra and with PO4 or AsO4 tetrahedra (T). The structures differ in the linkages through the Fe3+O6 octahedra, which produce different but closely related framework configurations. The structures contain two types of non-framework cation sites, which are designated A and B. In general, there are two or more A sites partially occupied by disordered, generally larger cations that are coordinated to O atoms in the framework and to H2O molecules. The B site is occupied by a smaller cation that is octahedrally coordinated to H2O molecules. The general formula for minerals with either the betpakdalite or the obradovicite structure is: [A2(H2O)nB(H2O)6][Mo8T2Fe3+3O30+7(OH)7–x], where x is the total charge of the cations in the A and B sites (+3 to +7) and n is variable, ideally 17 for arsenates and 15 for phosphates. The ideal total number of A cations is defined as 2 in the general formula, but varies from 1 to 3.8 in analysed samples. Dominant cations at the A site include K, Na and Ca and at the B site Na, Ca, Mg, Cu and Fe. The combinations that have been identified in this study define six new heteropolymolybdate species.

A suffix-based nomenclature scheme is established for minerals of the betpakdalite, mendozavilite and obradovicite groups, with the following root names based on the structure types and the T-site cations: betpakdalite (T = As), mendozavilite (T = P) and obradovicite (T = As). Two suffixes of the form -AB, corresponding to the dominant cations in the two different types of non-framework cation sites complete the species name. The historical name melkovite is retained rather than introducing mendozavilite-CaCa.

Our investigation of the paramendozavilite type specimen revealed no paramendozavilite, but an apparently closely related new mineral; however, another sample of paramendozavilite analysed had K > Na.

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–.

Natropharmacoalumite, ideally NaAl4[(OH)4(AsO4)3]·4H2O, is a new mineral from the Maria Josefa Gold mine, Rodalquilar, Andalusia region, Spain. It occurs as colourless, intergrown cubic crystals with chenevixite, kaolinite, jarosite and indeterminable mixtures of Fe and Sb oxyhydroxides. Individual crystals are up to 0.5 mm on edge, although crystals are more commonly ˜0.25 mm across and occur in patchy aggregates several millimetres across. The mineral is transparent with a vitreous to adamantine lustre. It is brittle with an imperfect cleavage, irregular fracture and a white streak. The Mohs hardness is ˜2.5 with a calculated densityof 2.56 g cm–3 for the empirical formula. Electron microprobe analyses yielded Na2O 2.52%, K2O 1.49%, Al2O3 29.50%, As2O5 48.84% and H2O was calculated in line with the structural analysis as 16.28% totalling 98.63%. The empirical formula, based upon 20.21 oxygen atoms, is [Na0.57K0.22(H3O)0.21]Σ1.00Al4.05(As2.97O12)(OH)4·4H2O. The five strongest lines in the X-ray powder diffraction pattern are [dobs(Å), Iobs,(hkl)]: 7.759,100,(100); 4.473,40,(111); 3.870,50,(200); 2.446,9,(301); 2.331,12,(311). Natropharmacoalumite is cubic, space group with a = 7.7280(3) Å, V = 461.53(3) Å3 and Z = 1. The crystal structure was solved by direct methods and refined to R1 = 0.063 for 295 reflections with F>4σ(F). The structure conforms broadly to that of the general pharmacosiderite structure type, with Na as the dominant cation in cavities of strongly distorted Al octahedra and As tetrahedra. A new group nomenclature system for minerals with the pharmacosiderite structure has been established, including the renaming of aluminopharmacosiderite to pharmacoalumite.

The crystal structure of chloroxiphite, Pb3CuO2(OH)2Cl2, from Merehead Quarry (monoclinic, P21/m, a = 6.6972(8), b = 5.7538(5), c = 10.4686(14) Å,β = 97.747(10)°, V = 399.72(8) Å3) has been refined to R1 = 0.041. The structure contains three symmetrically unique Pb sites and one Cu site. The strong distortion of the Pb2+ coordination polyhedra is due to the stereoactivity of the s2 lone electron pairs on the Pb2+ cations. The Cu-site is coordinated by four OH- groups to form an almost planar Cu(OH)4 square that is complemented by two apical Cl– anions, forming an elongated [Cu(OH)4Cl2] octahedron. Because of the large size and variability of coordination polyhedra around Pb2+ cations and the strength of the Me–O bonds in comparison to the Me–Cl bonds (Me = metal), it is convenient to describe the structure of chloroxiphite in terms of oxocentred OPb4 tetrahedra. The O1 atom is tetrahedrally coordinated by four Pb2+ cations forming relatively short and strong O–Pb bonds. The OPb4 tetrahedra link together via common edges to form [O2Pb3]2+ double chains. The difference between chloroxiphite and other natural oxyhalides is the presence of Cu2+ cations which form an independent structural unit that links to units formed by OPb4 tetrahedra. In this sense, chloroxiphite can be considered as a modular structure consisting of both strong cation- and anion-centred units.

Background: Granulomatosis with polyangitis (GPA) is a rare systemic vasculitis with a prevalence of 0.6 per million in the pediatric population. CNS involvement occurs in 7-18% of cases. Pituitary involvement is only noted in 1% of cases. Methods: A 16-year-old girl with newly-diagnosed GPA presented to our hospital with progressive debilitating headaches, polyuria, and polydipsia. Results: Initial MRI showed changes to the pituitary. Lumbar puncture (LP) revealed opening pressure of 26. She developed central diabetes insipidus (DI) and visual changes. Repeat head imaging showed adenohypophysitis. The GPA was previously treated with steroids and cyclophosphamide, followed by Cellcept. Once the pituitary involvement was discovered, she was given re-induction therapy with Rituximab and steroid dose was increased. DI is being treated with DDAVP. Her headaches are improving. Conclusions: CNS inflammatory diseases are rare in childhood. Pituitary involvement is extremely rare in GPA. Induction therapy for adults with GPA and pituitary involvement includes glucocorticoids and cyclophosphamide, which often leads to improvement of MRI abnormalities but is not effective in resolving pituitary dysfunction. Our patient had already received this treatment when she developed the CNS findings. This case demonstrates that cerebral involvement is often resistant to classic therapy, and one should be vigilant in looking for CNS inflammation in these patients.

The Kabwe Zn-Pb deposit (central Zambia) consists of a cluster of mixed sulfide and non-sulfide orebodies. The sulfide ores comprise sphalerite, galena, pyrite, chalcopyrite and accessory Ge-sulfides (±Ga and In). The non-sulfide ores comprise: (1) willemite-dominated zones encasing massive sulfide orebodies and (2) oxide-dominated alteration bands, overlying both the sulfide and Zn-silicate orebodies. This study focuses on the Ge, In and Ga distribution in the non-sulfide mineralization, and was carried out on a suite of Kabwe specimens, housed in the Natural History Museum Ore Collection (London). Petrography confirmed that the original sulfides were overprinted by at least two contrasting oxidation stages dominated by the formation of willemite (W1 and W2), and a further event characterized by weathering-related processes. Oxygen isotopic analyses have shown that W1 and W2 are unrelated genetically and furthermore not related to supergene Zn-Pb-carbonates in the oxide-dominated assemblage. The δ18O composition of 13.9–15.7‰ V-SMOW strongly supports a hydrothermal origin for W1. The δ18O composition of W2 (−3.5‰ to 0‰ V-SMOW) indicates that it precipitated from groundwaters of meteoric origin in either a supergene or a low-T hydrothermal environment. Gallium and Ge show a diversity of distribution among the range of Zn-bearing minerals. Gallium has been detected at the ppm level in W1, sphalerite, goethite and hematite. Germanium occurs at ppm levels in W1 and W2, and in scarcely detectable amounts in hemimorphite, goethite and hematite. Indium has low concentrations in goethite and hematite. These different deportments among the various phases are probably due to the different initial Ga, In and Ge abundances in the mineralization, to the different solubilities of the three elements at different temperatures and pH values, and finally to their variable affinities with the various minerals formed.

Hemihedrite from the Florence Lead-Silver mine in Pinal County, Arizona, USA was first described and assigned the ideal chemical formula Pb10Zn(CrO4)6(SiO4)2F2, based upon a variety of chemical and crystal-structure analyses. The primary methods used to determine the fluorine content for hemihedrite were colorimetry, which resulted in values of F that were too high and inconsistent with the structural data, and infrared (IR) spectroscopic analysis that failed to detect OH or H2O. Our reinvestigation using electron microprobe analysis of the type material, and additional samples from the type locality, the Rat Tail claim, Arizona, and Nevada, reveals the absence of fluorine, while the presence of OH is confirmed by Raman spectroscopy. These findings suggest that the colorimetric determination of fluorine in the original description of hemihedrite probably misidentified F due to the interferences from PO4 and SO4, both found in our chemical analyses. As a consequence of these results, the study presented here proposes a redefinition of the chemical composition of hemihedrite to the ideal chemical formula Pb10Zn(CrO4)6(SiO4)2(OH)2. Hemihedrite is isotypic with iranite with substitution of Zn for Cu, and raygrantite with substitution of Cr for S. Structural data from a sample from the Rat Tail claim, Arizona, indicate that hemihedrite is triclinic in space group P1, a = 9.4891(7), b = 11.4242(8), c = 10.8155(7) Å, α = 120.368(2)°, β = 92.017(3)°, γ = 55.857(2)°, V = 784.88(9) Å3, Z= 1, consistent with previous investigations. The structure was refined from singlecrystal X-ray diffraction data to R1 = 0.022 for 5705 unique observed reflections, and the ideal chemical formula Pb10Zn(CrO4)6(SiO4)2(OH)2 was assumed during the refinement. Electron microprobe analyses of this sample yielded the empirical chemical formula Pb10.05(Zn0.91Mg0.02)∑ = 0.93(Cr5.98S0.01P0.01)∑ = 6.00 Si1.97O34H2.16 based on 34 O atoms and six (Cr + S + P) per unit cell.

A new protocol for the quantitative determination of zeolite-group mineral compositions by electron probe microanalysis (wavelength-dispersive spectrometry) under ambient conditions, is presented. The method overcomes the most serious challenges for this mineral group, including new confidence in the fundamentally important Si-Al ratio. Development tests were undertaken on a set of natural zeolite candidate reference samples, representing the compositional extremes of Na, K, Cs, Mg, Ca, Sr and Ba zeolites, to demonstrate and assess the extent of beam interaction effects on each oxide component for each mineral. These tests highlight the variability and impact of component mobility due to beam interaction, and show that it can be minimized with recommended operating conditions of 15 kV, 2 nA, a defocused, 20 μm spot size, and element prioritizing with the spectrometer configuration. The protocol represents a pragmatic solution that works, but provides scope for additional optimization where required. Vital to the determination of high-quality results is the attention to careful preparations and the employment of strict criteria for data reduction and quality control, including the monitoring and removal of non-zeolitic contaminants from the data (mainly Fe and clay phases). Essential quality criteria include the zeolite-specific parameters of R value (Si/(Si + Al + Fe3+), the 'E%' charge-balance calculation, and the weight percent of non-hydrous total oxides. When these criteria are applied in conjunction with the recommended analytical operating conditions, excellent inter-batch reproducibility is demonstrated. Application of the method to zeolites with complex solid-solution compositions is effective, enabling more precise geochemical discrimination for occurrence-composition studies. Phase validation for the reference set was conducted satisfactorily with the use of X-ray diffraction and laser-ablation inductively-coupled plasma mass spectroscopy.

Yeomanite, Pb2O(OH)Cl, is a new Pb-oxychloride found in the manganese pod mineral assemblage at Merehead (Torr Works) Quarry, near Cranmore, Somerset, England. Yeomanite is named in joint recognition of Mrs Angela Yeoman (1931–) and her company, Foster Yeoman, who operated Merehead Quarry for aggregate until 2006. The mineral is normally white, occasionally grey, with a white streak and a vitreous to transparent lustre. Invariably intimately associated with mendipite, yeomanite appears to be formed of small, twisted, rope-like fibres growing from the end of columnar mendipite masses, forming loose mats and strands resembling asbestos. Individual fibres are generally <8 mm long, but exceptionally may reach up to 15 mm. There is a perfect cleavage parallel to the long axis of the fibres but this is masked by the fibrous nature, especially as individual fibres break easily. The Dcalc for the ideal formula is 7.303 g/cm3. The mean RI in air at 589 nm is 2.27. The eight strongest reflections in the powder X-ray diffraction pattern [(d in Å) (Intensity) (hkl)] are: 2.880(100)(113); 2.802(78)(006); 3.293(61)(200); 3.770(32)(011); 2.166(22)(206); 1.662(19)(119); 2.050(18)(303); 3.054(17)(105) Yeomanite is orthorhombic, Pnma, a = 6.585(10), b = 3.855(6), c = 17.26(1) Å, V = 438(1) Å3, Z = 4. Yeomanite is a new example of the growing family of lead oxychloride minerals that have a structure based upon oxocentred OPb4 tetrahedra, which, in this mineral, jointly with OHPb3 triangles, form [O(OH)Pb2]+ chains similar to those observed in synthetic Pb2O(OH)I. Yeomanite is structurally related to sidpietersite, penfieldite and laurionite.

In the limit of an asymptotically large diffusivity ratio of order $\mathcal{O}$(ϵ−2) ≫ 1, steady-state spatially periodic patterns of localized spots, where the spots are centred at lattice points of a Bravais lattice, are well-known to exist for certain two-component reaction–diffusion systems (RD) in $\mathbb{R}$2. For the Schnakenberg RD model, such a localized periodic spot pattern is linearly unstable when the diffusivity ratio exceeds a certain critical threshold. However, since this critical threshold has an infinite-order logarithmic series in powers of the logarithmic gauge ν ≡ −1/log ϵ, a low-order truncation of this series is expected to be in rather poor agreement with the true stability threshold unless ϵ is very small. To overcome this difficulty, a hybrid asymptotic-numerical method is formulated and implemented that has the effect of summing this infinite-order logarithmic expansion for the stability threshold. The numerical implementation of this hybrid method relies critically on obtaining a rapidly converging infinite series representation of the regular part of the Bloch Green's function for the reduced-wave operator. Numerical results from the hybrid method for the stability threshold associated with a periodic spot pattern on a regular hexagonal lattice are compared with the two-term asymptotic results of [10] (Iron et al. J. Nonlinear Science, 2014). As expected, the difference between the two-term and hybrid results is rather large when ϵ is only moderately small. A related hybrid method is devised for accurately approximating the stability threshold associated with a periodic pattern of localized spots for the Gray-Scott RD system in $\mathbb{R}$2.