Fluoro-potassic-pargasite, ideally AKBCa2C(Mg4Al) (Si6Al2)O22WF2, a new amphibole species, has been found in a skarn in the Tranomaro area, Madgascar. The sample used for the description of the new mineral species is a large single amphibole crystal, 4 mm × 2 mm × 2 cm in size, brownish-black with brownish-yellow phlogopite lamellae adhering to one face of the crystal. Fluoro-potassic-pargasite is brittle, has a Mohs hardness of 6.5 and a splintery fracture; it is non-fluorescent, has perfect {110} cleavage, no observable parting, and has measured and calculated densities of 3.46 and 3.151 g cm−3, respectively. In plane-polarized light, it is pleochroic, X = colourless to very pale grey, Y = very pale grey, Z = colourless; X ^ a = 46.9° (in β obtuse), Y ‖ b, Z ^ c = 31.4° (in β acute). It is biaxial positive, α = 1.638(2), β = 1.641(2), γ = 1.653(2); 2Vobs = 49.6(4)°, 2Vcalc = 53.4°.

Fluoro-potassic-pargasite is monoclinic, space group C2/m, a = 9.9104(2), b = 17.9739(4), c = 5.3205(1) Å, β = 105.534(2)°, V = 913.11(6) Å3, Z = 2. The eight strongest lines in the X-ray powder-diffraction pattern are [d in Å(I)(hkl)]: 3.133(100)(310), 3.270(55)(240), 2.809(47)(330). 8.413(45)(110), 2.698(39)(151), 3.374(31)(131), 2.934(29)(221) and 1.647(29)(461). Electron microp-robe analysis gives SiO2 40.20, Al2O3 17.61, TiO2 0.46, FeO 1.96, Fe2O3 2.51, MgO 16.95, MnO 0.05, CaO 13.18, Na2O 0.99, K2O 3.72, F 2.75, H2Ocalc 0.77, sum 99.99 wt.%. The formula unit, calculated on the basis of 24 (O,OH,F) with (OH + F) = 2 - (2 × Ti), is A(K0.69Na0.28Ca0.04)∑=1.01BCa2.00C(Mg3.64Fe0.242+Mn0.01Al0.79Fe0.273+Ti0.05)∑=5.00T(Si5.80Al2.20)∑=8.00O22W[F1.26(OH)0.74]∑=2.00. The mineral species and name have been approved by the IMA CMNMC (IMA 2009-091).

Two crystals of Mg, Al-disordered quintinite-2H (Q1 and Q2), [Mg4Al2(OH)12](CO3)(H2O)3, from the Kovdor alkaline massif, Kola peninsula, Russia, have been characterized chemically and structurally. Both crystals have hexagonal symmetry, P63/mcm, a = 3.0455(10)/3.0446(9), c = 15.125(7)/15.178(5) Å, V = 121.49(8)/121.84(6) Å3. The structures of the two crystals have been solved by direct methods and refined to R1 = 0.046 and 0.035 on the basis of 76 and 82 unique observed reflections for Q1 and Q2, respectively. Diffraction patterns obtained using an image-plate area detector showed the almost complete absence of superstructure reflections which would be indicative of the Mg-Al ordering in metal hydroxide layers, as has been observed recently for other quintinite polytypes. The crystal structures are based on double hydroxide layers [M(OH)2] with an average disordered distribution of Mg2+ and Al3+ cations. Average <M–OH> bond lengths for the metal site are 2.017 and 2.020 Åfor Q1 and Q2, respectively, and are consistent with a highly Mg-Al disordered, average occupancy. The layer stacking sequence can be expressed as …=AC=CA=…, corresponding to a Mg-Al-disordered 2H polytype of quintinite. The observed disorder is probably the result of a relatively high temperature of formation for the Q1 and Q2 crystals compared to ordered polytypes. This suggestion is in general agreement with the previous observations which demonstrated, for the Mg-Al system, a higher-temperature regime of formation of the hexagonal (or pseudo-hexagonal in the case of quintinite-2H-3c) 2H polytype in comparison to the rhombohedral (or pseudo-rhombohedral in the case of quintinite-1M) 3R polytype.

To determine the mechanism of acid-leaching of ilmenite to ultimately forming rutile, we have carried out an experimental study of ilmenite alteration in autoclaves at 150ºC in HCl solutions. The resulting products were studied by X-ray diffraction, scanning electron microscopy, electron microprobe and Raman spectroscopy. In some experiments the solution was initially enriched in 18O and the distribution of the isotope in the alteration products mapped from the frequency shift of cation oxygen stretching bands in the Raman spectra. The alteration begins at the original ilmenite crystal surface and has also taken place along an intricate branching network of fractures in the ilmenite, generated by the reaction. Element-distribution maps and chemical analyses of the reaction product within the fractures show marked depletion in Fe and Mn and a relative enrichment of Ti. Chemical analyses however, do not correspond to any stoichiometric composition, and may represent mixtures of TiO2 and Fe2O3. The fracturing is possibly driven by volume changes associated with dissolution of ilmenite and simultaneous reprecipitation of the product phases (including rutile) from an interfacial solution along an inward moving dissolution-reprecipitation front. Raman spectroscopy shows that the 18O is incorporated in the rutile structure during the recrystallization. Throughout the alteration process, the original morphology of the ilmenite is preserved although the product is highly porous. The rutile inherits crystallographic information from the parent ilmenite, resulting in a triply-twinned rutile microstructure. The results indicate that the ilmenite is replaced directly by rutile without the formation of any intermediate reaction products. The reaction is described in terms of an interface-coupled dissolution-precipitation mechanism.

Noonkanbahite, ideally BaKNaTi2(Si4O12)O2, is described as a new mineral species. At Liley [Löhley], Eifel Mountains, Germany (the holotype locality), it occurs as sprays of prismatic crystals (up to 8 mm) or single prismatic crystals (up to 4 mm) on walls of cavities in alkaline igneous rocks. At Murun, Siberia, Russia, noonkanbahite forms coarse lamellar crystals up to 0.05 cm × 0.7 cm × 1.5 cm embedded in kalsilite syenite. Noonkanbahite is brittle, H = 6, Dobs. = 3.39(1), Dcalc. = 3.49 g/cm3, has a vitreous lustre and does not fluoresce in ultraviolet light. It has poor cleavage on {010} and {100} and weak parting on {011}. Noonkanbahite is biaxial positive with 2Vobs. = 75(2)°, 2Vcalc. = 72.7(9)°, α 1.730(5), β 1.740(5) and γ 1.765(5), dispersion is medium, r < v. In transmitted plane-polarized light, noonkanbahite is strongly pleochroic, with X colourless, Y yellowish, Z straw-yellow; X = a, Y = b, Z = c. Noonkanbahite is orthorhombic, space group Imma, a = 8.0884(4), b = 10.4970(5), c = 13.9372(6) Å, V = 1183.3(1) Å3, Z = 4. The strongest ten X-ray diffraction lines in the powder pattern [d in Å (I)(hkl)] are: 2.907(100)(222), 8.353(50)(001), 3.196(50)(220), 2.097(50)(242), 2.241(40)(215), 2.179(40)(035), 3.377(30)(031), 2.694(30)(015), 2.304(30)(233), and 1.564(30)(064). Electron microprobe analysis gives SiO2 37.82, TiO2 15.54, ZrO2 0.42, Nb2O5 3.18, Al2O3 0.17, Fe2O3 (recalculated from FeO) 5.63, MnO 0.32, MgO 0.53, BaO 20.60, CaO 1.36, K2O 5.32, Na2O 6.14, F 0.78, H2O 0.58, sum 98.39 wt.%, (H2O determined by SIMS). The formula unit, calculated on the basis of 14 anions (O+OH+F), is (Ba0.85K0.13)Σ0.98(K0.59Na0.26Ca0.15)Σ1.00Na(Ti1.23Fe0.453+Nb0.15Mg0.08Mn0.03Zr0.02Al0.01)Σ1.97 (Si3.99Al0.01O12)(O1.33OH0.41F0.26)Σ2.00, Z = 4.

The crystal structure was refined to R1 = 2.8% for 970 unique (F0 > 4σF) reflections collected on a Bruker single-crystal P4 diffractometer with a CCD detector and MoKα X-radiation. The crystal structure of noonkanbahite is isostructural with that of batisite, ideally BaNa2Ti2(Si4O12)O2, and scherbakovite, ideally K2NaTi2(Si4O12)O(OH). There are two octahedrally coordinated sites, M(1) and M(2), occupied by (Ti1.23Fe0.453+Nb0.15Mg0.08Mn0.03Zr0.02Al0.01), ideally Ti2 a.p.f.u. There are three interstitial A sites, [9]A(1), [8]A(2) and [6]A(3), occupied by Ba, K and Na, respectively. Si tetrahedra and M octahedra form a framework with interstitial cages occupied by Ba, K and Na atoms at the A sites. Noonkanbahite, BaKNaTi2(Si4O12)O2, is a K analogue of batisite, BaNa2Ti2(Si4O12)O2, and a Ba analogue of shcherbakovite, K2NaTi2(Si4O12)O(OH).

Metastable authigenic 1M illite from shale of diagenetic grade has been studied using a high-resolution transmission electron microscope (HRTEM) equipped with energy-dispersive spectrometer, X-ray diffraction, and scanning electron microscope. The illite occurs as deformed flakes deficient in interlayer K+ cations with 0.6 per half cell, and with abnormally high Al in both octahedral and tetrahedral sites. Complex structural adjustments reflecting the unusual chemical composition are observed in images of illite at near-atomic resolution. Different distances and directions of intralayer shift between the upper tetrahedral sheet and the lower tetrahedral sheet within 2:1 layers are found in this sample. Intralayer undershift structure coupled with interlayer displacement is found in a 1M illite crystal, and intralayer overshift structure coupled with no interlayer displacement is found in a 1M domain of a larger crystal. Two tetrahedral sheets across the interlayer region sometimes deviate from ideal positions causing interlayer displacement. Two pyrophyllite layers are found overlying a stack of ordered 1M illite layers, and are overlain by illite layers with anomalous interlayer offsets. This offset is considered to result from an increase in the lateral dimensions of the tetrahedral sheet due to anomalous high Al content. Our observation of intralayer and interlayer deficiencies indicate that authigenic illite that crystallized in the early stage of diagenesis at low temperatures tends to give rise to heterogeneous, disordered, and metastable structures.

Arisite-(La), ideally NaLa2(CO3)2[F2x(CO3)1–x]F, is a new layered REE-fluorcarbonate mineral from miarolitic cavities within the Aris phonolite, Namibia (IMA no. 2009-019). It occurs as distinct chemical zones mixed with its Ce-analogue, arisite-(Ce). Crystals are vitreous, transparent beige, beige-yellow, light lemon-yellow to pinkish, and occur as tabular prisms up to 1.5 mm. Arisite-(La) is brittle, has conchoidal fracture, poor cleavage perpendicular to (001), a Mohs hardness of ~3–3½, is not fluorescent in either long- or shortwave UV radiation, dissolves slowly in dilute HCl at room temperature and sinks in methylene iodide, Dcalc. = 4.072 g cm–3. Arisite-(La) is uniaxial negative, has sharp extinction, with both ω and ε exhibiting a range of values within each grain: ω = 1.696–1.717(4) and ε = 1.594–1.611(3), a result of chemical zoning attributed to both Ce ⇌ La and Na ⇌ Ca substitutions. The crystal structure of both arisite-(Ce) and arisite-(La) were solved by direct methods and refined to R = 1.66%, wR2 = 4.31% (Ce) and R = 2.09%, wR2 = 5.26% (La), respectively. Arisite is hexagonal, Pm2, Z = 1, with unit-cell parameters of a = 5.1109(2) Å, c = 8.6713(4) Å, V = 196.16(6) Å3 for arisite-(Ce), and a = 5.1131(7) Å, c = 8.6759(17) Å, V = 196.43(5) Å3 for arisite-(La). Arisite-(Ce) and arisite-(La) are members of the layered, flat-lying REE-fluorcarbonate group which have crystal structures characterized by separate layers of triangular planar groups that parallel the overall layering of the structure, F, REE and alkali or alkaline-earthelements. Overall, the arisite structure can be defined by three distinct layers which parallel (001): (1) ∞[REE(CO3)2F] slabs, (2) sheets of Naϕ9 polyhedra, and (3) ∞[2F/CO3]2–. Based on its (M+F)/C ratio, arisite can further be described as having a dense, flat-lying fluorcarbonate structure, a classification which includes the structurally related mineral species cordylite, kukharenkoite, cebaite, lukechangite, huanghoite, and one incompletely characterized synthetic phase, NaY2(CO3)3F.

The previously unknown crystal structure of mckinstryite, originally described as Ag1.18Cu0.82S or (Ag,Cu)2S, was solved and refined using single-crystal X-ray diffractometer data collected from a sample from the Clara mine, Black Forest (Mo-Kα radiation, CCD area detector, R1(F) = 3.85%). Mckinstryite has the refined formula Ag4.92Cu3.08S4 or Ag1.23Cu0.77S (idealized Ag5Cu3S4 or Ag1.25Cu0.75S) and crystallizes in space group Pnma (no. 62), with a = 14.047(3) Å, b = 7.805(2) Å , c = 15.691(3) Å, V = 1720.3(7) Å3, Z = 8. The structure contains five Ag, six Cu and eight S sites in the asymmetric unit. One of the Ag sites shows minor Cu-for-Ag substitution. The topology is based on flat, interrupted (010) layers of Cu and S atoms (all atoms on y = 0.25), in which the Cu atoms show triangular or two-coordination to S (interrupted {6,3} tiling). These layers alternate with uneven layers consisting of Ag atoms showing irregular three- to two-coordination to S. Some fairly short Ag–Cu contact distances (2.781–2.884 Å) strongly indicate that metal-metal interaction plays an important role in mckinstryite. The topology is related to that of stromeyerite (∼AgCuS) which contains complete flat layers of Cu atoms triangularly coordinated to S atoms, alternating with layers of loosely packed Ag atoms.

A critical evaluation of literature data on the chemical composition and unit-cell parameters of mckinstryite confirms the presence of a small compositional range of mckinstryite which extends approximately from Ag1.18Cu0.82S to Ag1.25Cu0.75S, with the presently studied sample being fairly Agrich. The accurate limits of this range at ambient temperature are still to be determined.

Turkestanite, a rare Th- and REE-bearing cyclosilicate in the ekanite–steacyite group was found in evolved peralkaline granitesfrom the Morro Redondo Complex, south Brazil. It occurswith quartz, alkali feldspar and an unnamed Y-bearing silicate. Electron microprobe analysis indicates relatively homogeneous compositions with maximum ThO2, Na2O and K2O contentsof 22.4%, 2.93% and 3.15 wt.%, respectively, and significant REE2O3 abundances(5.21 to 11.04 wt.%). The REE patterns show enrichment of LREE over HREE, a strong negative Eu anomaly and positive Ce anomaly, the latter in the most transformed crystals. Laser ablation inductively coupled plasma mass spectrometry trace element patterns display considerable depletions in Nb, Zr, Hf, Ti and Li relative to whole-rock sample compositions. Observed compositional variations suggest the influence of coupled substitution mechanisms involving steacyite, a Na-dominant analogue of turkestanite, iraqite, a REE-bearing end-member in the ekanite–steacyite group, ekanite and some theoretical end-members. Turkestanite crystals were interpreted as having precipitated during post-magmatic stages in the presence of residual HFSE-rich fluidscarrying Ca, the circulation of which wasenhanced by deformational events.

Secondary phosphate assemblages from the Hagendorf Süd granitic pegmatite, containing the new Mn-Al phosphate mineral, nordgauite, have been characterized using scanning electron microscopy and electron microprobe analysis. Nordgauite nodules enclose crystals of the jahnsite—whiteite group of minerals, showing pronounced compositional zoning, spanning the full range of Fe/Al ratios between jahnsite and whiteite. The whiteite-rich members are F-bearing, whereas the jahnsite-rich members contain no F. Associated minerals include sphalerite, apatite, parascholzite, zwieselite-triplite solid solutions and a kingsmountite-related mineral. The average compositions of whiteite and jahnsite from different zoned regions correspond to jahnsite-(CaMnMn), whiteite-(CaMnMn) and the previously undescribed whiteite-(CaMnFe) end-members. Mo-Kα CCD intensity data were collected on a twinned crystal of the (CaMnMn)-dominant whiteite and refined in P2/a to wRobs = 0.064 for 1015 observed reflections.

The electrical conductivity of dry polycrystalline olivine compacts (hot-pressed and sintered pellets) was measured at pressures of 1.0–4.0 GPa, at temperatures of 1073–1423 K, and at different oxygen fugacities via the use of a YJ-3000t multi-anvil press. Oxygen fugacity was controlled successfully by means of five solid buffers: Fe3O4-Fe2O3, Ni-NiO, Fe-Fe3O4, Fe-FeO and Mo-MoO2. Within the selected frequency range of 102–106 Hz, the experimental results indicate that the grain interior conduction mechanism is characterized by a semi-circular curve on an impedance diagram. As a function of increasing pressure, the electrical conductivity of polycrystalline olivine compacts decreases, whereas the activation enthalpy and the temperature-independent pre-exponential factors increase slightly. The activation energy and activation volume of polycrystalline olivine compacts were determined to be 141.02±2.53 kJ/mol and 0.25±0.05 cm3/mol, respectively. At a pressure of 4.0 GPa, electrical conductivity was observed to increase as a function of increasing oxygen fugacity, and the relationship between electrical conductivity and oxygen fugacity can be described as log10 (σ) = (2.47±0.085) + (0.096±0.023)×log10fO2 + (–0.55±0.011)/T, which presents the exponential factor q (˜0.096). Our observations demonstrate that the primary conduction mechanism for polycrystalline olivine compacts is a small polaron.

Clasts of metamorphosed Cadomian granites from the ∼50—60 Ma Carpathian flysch in Gródek near the Rożnowskie Lake (Silesian Unit, SE Poland) are studied. They are considered to represent the Silesian Ridge, one of the hypothetical, currently unexposed source areas that supplied Carpathian sedimentary basins with clastic material. The gneisses preserve several examples of corona textures that include cores of primary monazite surrounded by polygonal grains of secondary apatite with thorianite inclusions, with intermediate zones of lamellar grains of secondary monazite and outermost rims of clay minerals, or various combinations thereof. Preservation of the complete textures is rare with polygonal apatite with thorianite inclusions, lamellar grains of monazite and clay minerals being particularly prevalent. Locally, polygonal apatite with thorianite inclusions surrounded by allanite and REE-epidote corona with a bastnasite-synchysite phase occurs also. The textures observed developed during primary monazite breakdown and replacement by secondary minerals. The variation in reaction products indicates that alteration was strictly dependent on the local chemical system.

The crystal structure of the sheet oxychloride mineral parkinsonite, nominally Pb7MoO9Cl2, has been determined for synthetic and natural crystals of analysed compositions, (Pb7.28Mo0.72) O8.96Cl1.96 and (Pb7.23Mo0.40V0.37)O8.90Cl1.82, respectively. Parkinsonite is tetragonal, space group I4/mmm. Unit-cell parameters for synthetic and natural crystals are: asynthetic = 3.9773(4) Å, csynthetic = 22.718(4) Å, Vsynthetic = 359.38(5) Å3, and anatural = 3.9570(3) Å, cnatural = 22.634(5) Å, Vnatural = 354.40(5) Å3. Final agreement indices (R1, wR2) for refinements of the two crystals are 0.024, 0.067 (synthetic) and 0.036, 0.078 (natural). Although a superlattice has been identified by electron diffraction for crystals of both samples (Welch et al., 1996), only the substructure could be determined by X-ray diffraction. This X-ray invisibility of the superstructure has also been observed for the closely related sheet oxychlorides asisite and schwartzembergite, for both of which superstructure motifs have been identified by electron diffraction. The Pb(1) site of both parkinsonite crystals is fully occupied by Pb. Refinement of the Pb content of the Pb(2) site for the synthetic and natural crystals gives occupancies of 0.85(1) and 0.70(1) respectively, corresponding to 3.40 and 2.80 Pb(2) a.p.f.u. respectively. The substituent cation Mo (synthetic crystal) and [Mo+V] (natural crystal) was located at a distance of 0.5 Å from Pb(2), being displaced along the fourfold axis. The reduced occupancy of Pb(2) is due to substitution by Mo or [Mo+V]. No evidence for separate Mo and V sites in the substructure of natural parkinsonite was found. Refined occupancies of the Cl site are 0.84(4) and 0.91(5) for the synthetic and natural crystals, respectively, and are consistent with the 9:1 superstructure component identified by electron diffraction.

In situ, high-temperature energy-dispersive X-ray powder diffraction (EDXRD) data have been collected on synthetic and a natural sample of mercury sulphide (HgS). These measurements were made between temperatures of 295 and 798 K. Synthetic samples of HgS were prepared by reaction between sulphide and mercury in aqueous solution. In a subsequently dried and aged synthetic HgS sample, heated in vacuo, there is a change from a poorly crystalline pseudocubic material into a well crystalline cubic material in the temperature region 583–623 K. At higher temperature (748 K), there is evidence for a partial phase transition to the high temperature hypercinnabar HgS structure. In a neoformed synthetic sample, heated in a sealed Ti container, the initial ‘pseudocubic’ metacinnabar phase partially transforms to a previously unknown phase (XHgS) in the temperature range 467–522 K. This phase disappears at 527 K, and the metacinnabar phase changes to a well crystalline cubic phase; cinnabar develops at 542 K. The proportion of cinnabar continues to increase up to 647 K. Both metacinnabar and cinnabar phases are retained on cooling. No phase transitions were observed for the natural cinnabar sample.

Kurilite, with the simplified formula, Ag8Te3Se, is a new mineral from the Prasolovskoe epithermal Au-Ag deposit, Kunashir Island, Kuril arc, Russian Federation. It occurs as aggregates up to 2 mm in size, composed of brittle xenomorphic grains, up to several μm in size, in quartz, associated with tetrahedrite, hessite, sylvanite and petzite. Kurilite is opaque, grey, with a metallic lustre and a black streak. Under plane-polarized light, kurilite is white with no observed bireflectance, cleavage, or parting observed. Under crossed polars it appears isotropic without internal reflections. Reflectance values in air and in oil, are tabulated. It has a mean VHN (25 g load) of 99.9 kg/mm2 which equates roughly to a Mohs hardness of 3. Electron microprobe analyses yield a mean composition of Ag 63.71, Au 0.29, Te 29.48, Se 5.04, S 0.07, total 98.71 wt.%. The empirical formula (based on 12 atoms) is (Ag7.97Au0.02)Σ7.99Te3.00(Se0.86Te0.12S0.03)Σ1.01. The calculated density is 7.799 g/cm3 (based on the empirical formula and unit-cell parameters refined from single-crystal data). Kurilite is rhombohedral, R3 or , a 15.80(1), c 19.57(6) Å, V 4231(12)Å3, c:a 1.2386, Z = 15. Its crystal structure remains unsolved. The seven strongest lines of the X-ray powder-diffraction pattern [d in Å (I)(hkl)] are: 3.727(20)(131), 2.996(50)(232), 2.510(30)(226,422), 2.201(100)(128,416,342), 2.152(20)(603), 2.079(30)(253), 2.046(20)(336,434). The mineral is named after the locality.

The new, non-centrosymmetric chain silicate, K2.9Rb0.1ErSi3O9, was prepared by a high-temperature flux-growth technique, and its crystal structure was determined from single-crystal X-ray intensity data (Mo-Kα, 293 K) in space P1, with a = 6.672(1), b = 6.719(1), c = 6.725(1) Å, α = 108.87(3), β = 106.72(3), γ = 107.61(3)°, V = 245.82(6) Å3, Z = 1, R(F) = 2.81%. The compound represents a novel structure type. K2.9Rb0.1ErSi3O9 is characterized by a mixed octahedral-tetrahedral framework, in which each corner of the isolated ErO6 octahedron (<Er—O> = 2.26 Å) is linked to infinite [Si3O9] chains extending approximately along [111]. This connectivity results in a microporous character with two different, narrow channels that extend parallel to [111] and [100] and host K+ cations. The atomic arrangement is strongly pseudorhombohedral. A single-crystal Raman spectrum of K2.9Rb0.1ErSi3O9 is in agreement with the low space-group symmetry. Relations to minerals and synthetic compounds based on [Si3O9] chains are discussed, revealing that the geometry of the chain in K2.9Rb0.1ErSi3O9 is similar to that in pectolite, NaCa2[HSi3O9].

Crystal-structure analysis was used to identify crystals of Pb(C6H6O7)·H2O on a specimen of hematite pseudomorphous after magnetite from the Payύn Matrύ volcanic field, Mendoza Province, Argentina. The compound is triclinic, P, a = 6.3434(2), b = 6.4566(2), c = 12.0640(9) Å, α = 99.233(7), β = 102.810(7), γ = 101.562(7)° and Z=2. The crystal structure, refined to R1 = 0.0169 for 2021 reflections [Fo>4σ(F)], consists of a zig-zag chain of 9-coordinated Pb2+ atoms along b. Chains are linked together by citrate molecules to form thick irregular layers in the ab plane. The layers are linked together only by H bonds. The citrate molecule exhibits normal bond lengths and angles. The Pb2+ atom exhibits markedly lopsided coordination due to the 6s2 lone-electron-pair effect. The lone electron pairs on alternating sets of adjacent Pb2+ atoms in the chain point towards one another.

The formation of the Pb(C6H6O7)·H2O crystals was the result of specimen cleaning in citric acid. The cleaning solution was apparently contaminated through the dissolution of minor associated Pb-bearing species by the citric acid. It is important to be aware of the possibility that micro-crystals may be inadvertently grown on mineral specimens during chemical cleaning, to carefully and critically inspect paragenetic relationships especially when studying mineral specimens that may have been cleaned in chemical agents, and to be particularly aware of health risks when treating Pb-bearing minerals in aqueous citric acid solutions.

Bendadaite, ideally Fe2+Fe23+ (AsO4)2(OH)2·4H2O, is a new member of the arthurite group. It was found as a weathering product of arsenopyrite on a single hand specimen from the phosphate pegmatite Bendada, central Portugal (type locality). Co-type locality is the granite pegmatite of Lavra do Almerindo (Almerindo mine), Linópolis, Divino das Laranjeiras county, Minas Gerais, Brazil. Further localities are the Veta Negra mine, Copiapó province, Chile; Oumlil-East, Bou Azzer district, Morocco; and Pira Inferida yard, Fenugu Sibiri mine, Gonnosfanadiga, Medio Campidano Province, Sardinia, Italy.

Type bendadaite occurs as blackish green to dark brownish tufts (<0.1 mm long) and flattened radiating aggregates, in intimate association with an intermediate member of the scorodite–mansfieldite series. It is monoclinic, space group P21/c, with a = 10.239(3) Å, b = 9.713(2) Å, c = 5.552(2) Å, β = 94.11(2)°, V = 550.7(2) Å3, Z = 2. Electron-microprobe analysis yielded (wt.%): CaO 0.04, MnO 0.03, CuO 0.06, ZnO 0.04, Fe2O3 (total) 43.92, Al2O3 1.15, SnO2 0.10, As2O5 43.27, P2O5 1.86, SO3 0.03. The empirical formula is (Fe2+0.52Fe3+0.32☐0.16)Σ1.00(Fe3+1.89Al0.11)Σ2.00(As1.87P0.13)Σ2.00O8(OH)2.00·4H2O based on 2(As,P) and assuming ideal 8O, 2(OH), 4H2O and complete occupancy of the ferric iron site by Fe3+ and Al. Optically, bendadaite is biaxial, positive, 2Vest. = 85±4°, 2Vcalc. = 88°, with α 1.734(3), β 1.759(3), γ 1.787(4). Pleochroism is medium strong: X pale reddish brown, Y yellowish brown, Z dark yellowish brown; absorption Z > Y > X, optical dispersion weak, r > v. Optical axis plane is parallel to (010), with X approximately parallel to a and Z nearly parallel to c. Bendadaite has vitreous to sub-adamantine luster, is translucent and non-fluorescent. It is brittle, shows irregular fracture and a good cleavage parallel to {010}. Dmeas. 3.15±0.10 g/cm3, Dcalc. 3.193 g/cm3 (for the empirical formula). The five strongest powder diffraction lines [d in Å (I)(hkl)] are 10.22 (10)(100), 7.036 (8)(110), 4.250 (5)(111), 2.865 (4)(), 4.833 (3)(020,011). The d spacings are very similar to those of its Zn analogue, ojuelaite. The crystal structure of bendadaite was solved and refined using a crystal from the co-type locality with the composition (Fe2+0.95☐0.05)Σ1.00(Fe3+1.80Al0.20)Σ2.00(As1.48P0.52)Σ2.00O8(OH)2·4H2O (R = 1.6%), and confirms an arthurite-type atomic arrangement.

Hydroniumpharmacosiderite, ideally (H3O)Fe4(AsO4)3(OH)4·4H2O, is a new mineral from Cornwall, UK, probably from the St. Day group of mines. It occurs as a single yellowish green, slightly elongated cube, measuring 0.17 mm ×0.14 mm ×0.14 mm. The mineral is transparent with a vitreous lustre. It is brittle with a cleavage on {001}, has an irregular fracture, a white streak and a Mohs hardness of 2–3 (determined on H3O-exchanged pharmacosiderite). Hydroniumpharmacosiderite has a calculated density of 2.559 g cm–3 for the empirical formula. The empirical formula, based upon 20.5 oxygen atoms, is: [(H3O)0.50K0.48Na0.06]1.04(Fe3.79Al0.22)4.01[(As2.73P0.15)2.88O12](OH)4·4H2.14O. The five strongest lines in the X-ray powder diffraction pattern are [dobs(Å),Iobs,(hkl)]: 8.050,100,(001); 3.265,35,(112); 2.412,30,(113); 2.830,23,(202); 4.628,22,(111). Hydroniumpharmacosiderite is cubic, space group with a = 7.9587(2) Å, V = 504.11(2) Å3 and Z = 1. The crystal structure was solved by direct methods and refined to R1 = 0.0481 for 520 reflections with I > 2σ(I). The structure is consistent with determinations for H3O-exhchanged pharmacosiderite and the general pharmacosiderite structure type.

Munakataite, Pb2Cu2(Se4+O3)(SO4)(OH)4, has been found in association with a variety of rare secondary Te minerals at Otto Mountain, San Bernardino County, California, USA. It is very rare and occurs as subparallel bundles of blue needles up to 1 mm long. Electron microprobe analyses provided the empirical formula Pb1.96Cu1.60[(Se0.894+S0.11)∑1O3](SO4)[(OH)3.34(H2O)0.66]∑4- Munakataite is mono-clinic, space group P21/m, with cell parameters a = 9.8023(26), b = 5.6751(14), c = 9.2811(25) Å, β = 102.443(6), V = 504.2(2) Å3 and Z = 2. The crystal structure, solved by direct methods and refined to R1 = 0.0308 for 544 Fo > 4σF reflections, consists of Jahn-Teller-distorted Cu2+O6 square bipyramids. which form chains along b by sharing trans edges across their square planes. The chains are decorated by SO4 tetrahedra and Se4+O3 pyramids, which bond to apical corners of adjacent bipyramids. The chains are linked to one another via bonds to two different PbO9 polyhedra, only one of which exhibits one-sided coordination typical of Pb2+ with a stereochemically active 6s2 lone-electron-pair. Munakataite is isostructural with schmiederite and the structure is closely related to that of linarite.