Philrothite, ideally TlAs3S5, is a new mineral from the Lengenbach quarry in the Binn Valley, Valais, Switzerland. It occurs as very rare crystals up to 200 mm across on realgar associated with smithite, rutile and sartorite. Philrothite is opaque with a metallic lustre and shows a dark brown streak. It is brittle; the Vickers hardness (VHN25) is 128 kg/mm2 (range: 120–137) (Mohs hardness of 3–3½). In reflected light philrothite is moderately bireflectant and weakly pleochroic from dark grey to light grey. Under crossed polars it is anisotropic with grey to bluish rotation tints. Internal reflections are absent. Reflectance percentages for the four COM wavelengths (Rmin and Rmax) are: 26.5, 28.8 (471.1 nm), 25.4, 27.2 (548.3 nm), 24.6, 26.3 (586.6 nm) and 24.0, 25.1 (652.3 nm), respectively.

Philrothite is monoclinic, space group P21/c, with a = 8.013(2), b = 24.829(4), c = 11.762(3) Å, β = 132.84(2)°, V = 1715.9(7) Å3, Z = 8. It represents the N = 4 homologue of the sartorite homologous series. In the crystal structure [R1 = 0.098 for 1217 reflections with I > 2σ(I)], Tl assumes tricapped prismatic sites alternating to form columns perpendicular to the b axis. Between the zigzag walls of Tl coordination prisms, coordination pyramids of As(Sb) form diagonally-oriented double layers separated by broader interspaces which house the lone electron pairs of these elements.

The eight strongest calculated powder-diffraction lines [d in Å(I/I0) (hkl)] are: 12.4145 (52) (020); 3.6768 (100) (61); 3.4535 (45) (131); 3.0150 (46) (53); 2.8941 (52) (81); 2.7685 (76) (230); 2.7642 (77) (34); 2.3239 (52) (092). A mean of five electron microprobe analyses gave Tl 26.28(12), Pb 6.69(8), Ag 2.50(4), Cu 0.04(2), Hg 0.07(2), As 32.50(13), Sb 3.15(3), S 26.35(10), total 97.58 wt.%, corresponding, on the basis of a total of nine atoms, to (Tl0.789Pb0.198)∑=0.987 (As2.662Sb0.159Ag0.142Cu0.004Hg0.002)∑=2.969S5.044. The new mineral has been approved by the Commission on New Minerals, Nomenclature and Classification (CNMNC) of the International Mineralogical Association (2013-066) and named for Philippe Roth (b. 1963), geophysicist and well known mineral expert on the Lengenbach minerals for more than 25 years.

Cobaltite-rich mineralization from the iron skarns of the Traversella magnetite mine (Western Alps, Italy) was studied by reflected-light microscopy, scanning electron microscopy and electron microprobe analysis. Cobaltite is found in carbonate-chlorite-rich rocks at the margins of the main magnetite masses, where it forms disseminations and metasomatic veinlets that postdate the formation of magnetite. The paragenesis includes cobaltite (± arsenopyrite), bismuthinite, pyrrhotite and/or pyrite, chalcopyrite, carbonates, talc, chlorite and native gold, and is indicative of a low-sulfidation environment. The sulfarsenides show oscillatory and sector zoning, which indicates disequilibrium during crystal growth. Compositional variations are mainly due to variations in the Co/Fe ratio of arsenopyrite and in either the Co/Fe or the Ni/(Fe + Co) ratios of the coexisting cobaltite. The Ni contents are low to very low in the cobaltites (<2.4 wt.%) and very low in the arsenopyrites (<0.16 wt.%). The As/S molar ratios in the cobaltites are highly variable (0.59−1.00) and show a broad negative correlation with the Fe contents. The formation of cobaltite is related to circulation of relatively low-temperature (<∼300°C), (Co,As,Bi)-rich fluids during the retrograde sulfidation stage which followed the formation of magnetite. The apparent restriction of cobaltite (+ bismuthinite ± arsenopyrite) to the margins of the main magnetite columns may reflect the establishment of thermochemical gradients around the main direction of infiltration of the retrograde metasomatic fluids.

The crystal structure of magbasite from the Eldor carbonatite complex, Quebec, Canada, has been determined and indicates that the currently accepted formula should be revised to KBaFe3+Mg7Si8O22(OH)2F6. Magbasite is orthorhombic, space group Cmme (Cmma), with unit-cell parameters a 18.9506(3) Å, b 22.5045(3) Å, c 5.2780(1) Å, V 2250.93(6) Å3 (Z = 4). The structure has been solved and refined to final agreement indices R1 = 0.026, wR2 = 0.052, GooF = 1.116 for a total of 2379 unique reflections, and is a new kind of trellis motif related to amphibole and carpholite topologies. An amphibole-like I-beam ‖(100) of edge-sharing octahedrally-coordinated M(1,2,3) sites, which are filled by Mg, is sandwiched between double-chains of SiO4 tetrahedra ‖c. This I-beam is connected to side-ribbons ‖(010) of edge-sharing (Mg,Fe2+)O4(OH,F)2 and Fe3+O4(OH)2 octahedra to form a tunnelled box or trellis structure very like that of carpholite, for which the I-beams are pyroxene-like. K occupies a tunnel site analogous to the A site of amphibole. Ba occupies a cavity site at the corners where the I-beam and side-ribbon meet, and corresponds to the A site of carpholite. The structural relations between magbasite and carpholite are discussed.

Cadmium sulfide mineralization occurs in grey-black shales of the late Mesoproterozoic Stoer Group, Torridonian Supergroup, northwest Scotland. Cadmium is strongly redox-controlled, and normally concentrated in anoxic marine sediments or epigenetic mineralization involving organic matter. However the Stoer Group was deposited in a terrestrial environment, including lacustrine deposits of shale. At the limited levels of atmospheric oxygenation in the Mesoproterozoic (∼10% of present), the near-surface environment could have fluctuated between oxic and anoxic, allowing fractionation of Cd from Zn, and the formation of Cd sulfide rather than Cd-bearing sphalerite. This occurrence emphasizes the importance of the Stoer Group as a record of the Mesoproterozoic terrestrial environment.

The crystal chemistry of a meso-octahedral Li,Be-bearing mica from the Harding pegmatite (Dixon, Taos County, New Mexico, USA) has been investigated by constant-wavelength single-crystal neutron diffraction at 20 K, single-crystal X-ray diffraction at 100 K and inductively coupled plasma-atomic emission spectrometry (ICP-AES). The chemical composition based on ICP-AES analysis leads to the following chemical formula (calculated on the basis of 12 oxygen atoms): Ca(Na0.26K0.04Ca0.69)∑0.99M(Li0.29Mg0.03Fe0.023+Al1.78)∑2.12T(Al1.73Be0.16Si2.11)S4.00O12H2.53. The apparent excess of H is probably due to the fact that the fraction of H2O was assumed by difference to 100 wt.%, and slightly overestimated. On the basis of the previous experimental findings on Li,Be-bearing mica, X-ray (at 100 K) and neutron (at 20 K) structure refinements were performed in the space groups Cc and C2/c. The neutron structure refinement in the space group Cc offers a view about the (Al,Be,Si)-tetrahedral ordering: the best fit of the refinement was reached with the T1 and T4 sites occupied by (Be + Al) and T2 and T3 fully occupied by Si. This leads to a final population of T(Al1.88Be0.12Si2.00)∑4.00 p.f.u., in reasonable agreement with the chemical analysis. The neutron refinement provides unambigous evidence of the occurrence of Li at the M1 site. The refined fraction of Li at the M1 site ranges between 0.27 and 0.29 a.p.f.u., in excellent agreement with the chemical analysis. The presence of Li, at least at a significant level, at the M2 (and M3) site can be ruled out, as a full site occupancy with the scattering length of Al was obtained. The location of the H sites and the complex hydrogen-bonding scheme are described. A comparison between the structure features of this Li,Be-mica and other brittle micas is carried out.

Acid mine drainage (AMD) commonly contains elevated concentrations of As(III) and/or As(V) due to oxidation of arsenic-containing sulfides. Bone char has been used as a low-cost filling material for passive treatment. The breakthrough curves of As(III) and As(V) were studied in column experiments conducted at different flow rates, adsorption cycle times, and with different coexisting cations and anions to compare their transport behaviours. The experimental data were fitted by the Convection- Diffusion Equation (CDE) and Thomas model with the aim of obtaining retardation factors of As(III) and As(V) and their maximum adsorption capacities, respectively. The maximum adsorption capacities of As(III) and As(V) are 0.214 and 0.335 mg/g, respectively. Coexisting Mn2+ and Al3+ ions can shorten the equilibrium time of As(V) adsorption from 25 h to 8 h, but they have little effect on As(III). The retardation factors of As(III) and As(V) calculated by the CDE model decrease with adsorption cycles from 37 to 20 and 51 to 32, respectively. The Mn2+ and Al3+ ions could enhance retention ability with adsorption cycle time, especially Mn2+ for As(V). Secondary adsorption phenomena were observed only in breakthrough curves of As(V) in the presence of Mn2+ and Al3+. The competitive influences of coexisting arsenic species is As(V) > As(III). Regeneration experiments using distilled water and NaOH solution were completed to quantify the degree of desorption of both As(III) and As(V). The results show that As(V) adsorbed on bone char has better desorption performance than As(III), and the average degrees of desorption of As(III) and As(V) for three desorption experiments are 75% and 31%, respectively.

Kidney stones consisting predominantly of whewellite (calcium oxalate monohydrate, COM) are often found attached to hydroxylapatite (HA) plaques that form in the soft tissue of kidneys, cause lesions and become exposed to urine. Although the processes of stone formation are not entirely known, it is an established view that so-called Randall’s plaques serve as substrates for COM crystal nucleation and growth from correspondingly supersaturated urine. However, the results presented here suggest an additional mineral replacement process is involved. In an experimental approach, HA was reacted in 0.25 mM, 0.5 mM and 1.0 mM oxalate solutions with pH ranging from 4.5 to 7.5, simulating normal to harsh conditions encountered in urine. Extremely acidic solutions induce dissolution of HA crystals coupled with re-precipitation of the released Ca2+ ions as COM on the HA surface. When, instead, bone was used as a substrate, being more similar to the pathological plaque (aggregated HA nanocrystals within an organic matrix), the HA-COM mineral-replacement reaction is induced even under much milder fluid conditions, commonly found in urine. Hence, a process of COM partly replacing and encrusting Randall’s plaque may take place in the urinary tract of idiopathic stone formers, representing a potential starting event for nephrolithiasis.

The new mineral species arsiccioite, AgHg2TlAs2S6, was discovered in the baryte-pyrite-iron oxide ore deposit exploited at the Monte Arsiccio mine, near Sant’Anna di Stazzema (Apuan Alps, Tuscany, Italy). It occurs as anhedral grains scattered in microcrystalline baryte, associated with cinnabar, laffittite, protochabournéite, pyrite, realgar, Hg-bearing sphalerite and stibnite. Arsiccioite is red, with a metallic to sub-metallic lustre. Minimum and maximum reflectance data for COM wavelengths in air are [λ (nm): R (%)]: 471.1: 29.0/29.4; 548.3: 27.6/28.3; 586.6: 26.1/26.5; 652.3: 24.2/24.6. Electron microprobe analyses give (wt.%): Cu 0.78(6), Ag 8.68(21), Zn 0.47(27), Fe 0.04(1), Hg 35.36(87), Cd 0.20(5), Tl 18.79(33), As 10.77(19), Sb 4.75(10), S 18.08(21), Se 0.07(5), total 97.99(44). On the basis of ΣMe = 6 a.p.f.u., the chemical formula is Ag0.87(2)Cu0.13(1)Zn0.08(4)Fe0.01(1)Hg1.91(5)Cd0.02(1)Tl1.00(2) (As1.56(2)Sb0.42(1))S1.98S6.12(6)Se0.01(1). Arsiccioite is tetragonal, I2m, with a 10.1386(6), c 11.3441(5) Å, V 1166.1(2) Å3, Z = 4. The main diffraction lines of the powder diagram are [d(in Å), visually estimated intensity, hkl]: 4.195, m, 211; 3.542, m, 103; 3.025, vs, 222; 2.636, m, 114; 2.518, s, 400 and 303. The crystal structure of arsiccioite has been refined by single-crystal X-ray data to a final R1 = 0.030, on the basis of 893 observed reflections. It shows a three dimensional framework of (Hg,Ag)- centred tetrahedra (1 M1 + 2 M2), with channels parallel to [001] hosting TlS6 and (As,Sb)S3 disymmetric polyhedra. Arsiccioite is derived from its isotype routhierite M1CuM2Hg2TlAs2S6 through the double heterovalent substitution M1Cu+ + M2Hg2+ → M1Hg2+ + M2Ag+. This substitution obeys a steric constraint, with Ag+, the largest cation relative to Hg2+ and Cu+, entering the largest M2 site. The ideal crystal chemical formula of arsiccioite is M1HgM2(Hg0.5Ag0.5)2TlAs2S6. The crystal chemistry of the routhierite isotypic series is discussed. Finally, the distribution of Hg ore minerals in the Apuan Alps is reviewed.

Klajite, MnCu4(AsO4)2(AsO3OH)2(H2O)10, the Mn-Cu-bearing member of the lindackerite group, was found in Jáchymov, Czech Republic, as the second world occurrence. It is associated with ondrušite and other arsenate minerals growing on the quartz gangue with disseminated primary sulfides, namely tennantite and chalcopyrite. Electron-microprobe data showed klajite aggregates to be chemically inhomogeneous at larger scales, varying from Mn-Ca-rich to Cu-rich domains. The chemical composition of the the Mn-rich parts of aggregates can be expressed by the empirical formula (Mn0.46Ca0.22Cu0.07Mg0.02)∑0.77(Cu3.82Mg0.14Ca0.03Zn0.01)∑4.00(As1.94Si0.06)∑2.00O8[AsO2.73(OH)1.27]2(H2O)10 (mean of seven representative spots; calculated on the basis of As + Si + P = 4 a.p.f.u. (atoms per formula unit) and 10 H2O from ideal stoichiometry), showing a slight cationic deficiency at the key Me-site. According to single-crystal X-ray diffraction, klajite from Jáchymov is triclinic, P, with a = 6.4298(8), b = 7.9716(8), c = 10.707(2) Å, α = 85.737(12)°, β = 80.994(13)°, γ = 84.982(10)°, and V = 538.85(14) Å3, Z = 1. The crystal structure was refined to R1 = 0.0628 for 1034 unique observed reflections (with Iobs > 3σ(I)), confirming that klajite (Mn-Cu member) and ondrušite (Ca-Cu member) are isostructural. The current data-set allowed determination of the positions of several hydrogen atoms. Discussion on hydrogen bonding networks in the structure of klajite as well as detailed bond-valence analysis are provided.

Putnisite, SrCa4Cr83+ (CO7)8SO4(OH)16·25H2O, is a new mineral from the Polar Bear peninsula, Southern Lake Cowan, Western Australia, Australia. The mineral forms isolated pseudocubic crystals up to 0.5 mm in size in a matrix composed of quartz and a near amorphous Cr silicate. Putnisite is translucent, with a pink streak and vitreous lustre. It is brittle and shows one excellent and two good cleavages parallel to {100}, {010} and {001}. The fracture is uneven and the Mohs hardness 1½−2. The measured density is 2.20(3) g/cm3 and the calculated density based on the empirical formula is 2.23 g/cm3. Optically, putnisite is biaxial negative, with α = 1.552(3), β = 1.583(3) and γ = 1.599(3) (measured in white light). The optical orientation is uncertain and pleochroism is distinct: X pale bluish grey, Y pale purple, Z pale purple. Putnisite is orthorhombic, space group Pnma, with a = 15.351(3), b = 20.421(4) Å, c = 18.270(4) Å, V = 5727(2) Å3 (single-crystal data), and Z = 4. The strongest five lines in the X-ray powder diffraction pattern are [d(Å)(I)(hkl)]: 13.577 (100) (011), 7.659 (80) (200), 6.667 (43) (211), 5.084 (19) (222, 230), 3.689 (16) (411). Electron microprobe analysis (EMPA) gave (wt.%): Na2O 0.17, MgO 0.08, CaO 10.81, SrO 5.72, BaO 0.12, CuO 0.29, Cr2O3 31.13, SO3 3.95, SiO2 0.08, Cl− 0.28, CO2calc 17.94, H2Ocalc 30.30, O=Cl−0.06, total 100.81. The empirical formula, based on O + Cl = 69, is: Cr8.023+Ca3.78Sr1.08Na0.11Cu0.072+Mg0.04Ba0.02[(SO4)0.96(SiO4)0.03]0.99 (CO3)7.98(OH)16.19Cl0.15·24.84H2O. The crystal structure was determined from single-crystal X-ray diffraction data (MoKα, CCD area detector and refined to R1 = 5.84% for 3181 reflections with F0 > 4σF. Cr(OH)4O2 octahedra link by edge-sharing to form an eight-membered ring. A 10-coordinated Sr2+ cation lies at the centre of each ring. The rings are decorated by CO3 triangles, each of which links by corner-sharing to two Cr(OH)4O2 octahedra. Rings are linked by Ca(H2O)4O4 polyhedra to form a sheet parallel to (100). Adjacent sheets are joined along [100] by corner-sharing SO4 tetrahedra. H2O molecules occupy channels that run along [100] and interstices between slabs. Moderate to weak hydrogen bonding provides additional linkage between slabs.

The 3.5 Ga Bon Accord Ni deposit occurs within the lowest serpentinized mafic–ultramafic lavas of the Barberton Greenstone Belt (South Africa). Though now completely mined out, it comprised a suite of rare Ni-rich minerals that led to its interpretation as either an extraterrestrial body or as an oxidized fragment of Fe-Ni alloy originating from the terrestrial core. In this study, we draw on detailed petrographic observation and mineral chemical data, as well as previous work, to re-evaluate these ideas. The balance of evidence, from thin section (<1 mm) to regional (∼10s of km) scales, appears to support an alternative origin for Bon Accord, possibly as an oxidized Ni-sulfide deposit formed in association with ocean floor komatiite eruptions.

Experiments in the system NaAlSiO4(Ne)−KAlSiO4(Ks)−SiO2(Qz)−H2O at 100 MPa show that the maximum content of NaAlSi2O6 in leucite is ∼4 wt.% and that analcime is close to the stoichiometric composition (NaAlSi2O6.H2O). Analcime forms metastably on quenching the higher-temperature experiments; it is secondary after leucite in experiments quenched from 780°C, while from 850°C it forms by alteration of leucite, and by devitrification of water-saturated glass. Both processes involve reaction with Na-rich aqueous fluids. Stable analcime forms at 500°C, well below the solidus, and cannot form as phenocrysts in shallow volcanic systems. New data for natural analcime macrocrysts in blairmorites are presented for the Crowsnest volcanics, Alberta, Canada. Other researchers have suggested that primary analcime occurs as yellow-brown, glassy, analcime phenocrysts. Our microprobe analyses show that such primary analcime is close to stoichiometric, with very low K2O (<0.1 wt.%), minor Fe2O3 (0.5−0.8 wt.%) and CaO (∼0.5 wt.%). An extrapolation of published experimental data for Ne−Ks−Qz at >500 MPa PH2O, where Anl + melt coexist, suggests that at >800 MPa two invariant points are present: (1) a reaction point involving Kf + Ab + Anl + melt + vapour; and (2) a eutectic with Kf + Anl + Ne + melt + vapour. We suggest that the nepheline-free equilibrium mineral assemblage for Crowsnest samples is controlled by reaction point (1). In contrast, blairmorites from Lupata Gorge, Mozambique, form at eutectic (2), consistent with the presence of nepheline phenocrysts. Our conclusions, based on high- vs. low-pressure experiments, confirm the suggestion made by other authors, that Crowsnest volcanic rocks must have been erupted explosively to preserve glassy analcime phenocrysts during very rapid, upward transport from deep in the crust (H2O pressures ≫500 MPa). Only rare examples survived the deuteric and hydrothermal alteration that occurred during and after eruption.

The new mineral therasiaite, ideally (NH4)3KNa2Fe2+Fe3+(SO4)3Cl5, was found in a mediumtemperature (∼250°C) intracrater active fumarole at La Fossa crater, Vulcano, Aeolian Islands, Sicily, Italy. It occurs on a pyroclastic breccia as brown to dark brown equant to short prismatic crystals up to 0.1 mm in length, in association with salammoniac, kremersite and adranosite. The mineral is monoclinic, space group: Cc (no. 9) with a = 18.284(4), b = 12.073(2), c = 9.535(2) Å, β = 108.10(3)°, V = 2000.6(7) Å3 and Z = 4. The six strongest reflections in the X-ray powder diffraction pattern are: [dobs in Å(I)(hkl)] 2.812(100)(23), 2.664(77)(13), 3.297(28)(33), 3.208(14)(2), 3.008(12)(040), 2.942(11)(331). The empirical formula (based on 17 anions per formula unit (p.f.u.)) is (NH4)2.68K1.32Na2.04Fe1.76Al0.12Mn0.12S2.98O11.95Cl5.05. The measured density is 2.41(1) g cm−3, dcalc = 2.395 g cm−3. The mineral is biaxial (−) with α= 1.585(3) β = 1.615(3) and γ = 1.630(3) (white light). Using single-crystal diffraction data, the structure was refined to a final R(F) = 0.0240 for 5574 independent observed reflections [I > 2σ(I)]. The structure of therasiaite displays a novel topology and contains two independent, distorted octahedral Fe sites, with the Fe atoms in oxidation state 3+ and 2+, respectively, each surrounded by three Cl atoms and three oxygens of the sulfate ions. The Fe octahedra and the three independent sulfate anions are connected to form chains running along [001]. Voids between the chains are occupied by three independent ammonium ions (partially replaced by K+), one K+ and two Na+ ions. The formula resulting from the structure refinement is [(NH4)2.25K0.75]KNa2Fe2(SO4)3Cl5.

The new mineral oskarssonite (IMA2012-088), with ideal formula AlF3, was found in August 2009 at the surface of fumaroles on the Eldfell volcano, Heimaey Island, Iceland (GPS coordinates 63°25′58.9″N 20°14′50.3″W). It occurs as sub-micron-sized crystals forming a white powder in association with anhydrite, bassanite, gypsum, jarosite, anatase, hematite, opal, ralstonite, jakobssonite and meniaylovite. Chemical analyses by energy-dispersive spectrometry with a scanning electronmicroscope produced the following mean elemental composition: Al, 31.70; F, 58.41; O, 9.22; total 99.33 wt.%. The empirical chemical formula is AlF2.6(OH)0.5 which suggests partial substitution of F by OH. Oskarssonite is rhombohedral, space group Rc, with ah = 4.9817(4) Å, c = 12.387(1) Å, Vuc = 266.23(5) Å3, Z = 6. The five strongest lines in the powder diffraction diagram [d in Å(I) (hkl)] are as follows: 3.54 (100) (012), 2.131 (13) (113), 1.771 (20) (024), 1.59 (15) (116), 1.574 (10) (122). Rietveld refinement confirms the identity of oskarssonite with the synthetic rhombohedral form of AlF3. Its structure can be described as a rhombohedral deformation of the idealized cubic perovskitetype octahedral framework of corner-sharing AlF6 groups. Oskarssonite appears in the surface part of the fumaroles where fluorides are abundant. At greater depths (below 10 cm) sulfates dominate among the fumarolic minerals. In accordance with its occurrence, we surmise that oskarssonite forms in the later stages of the fumarolic activity in an environment poor in alkalies and Mg. Ralstonite (NaxMgxAl1−xF3(H2O)y), which, unlike oskarssonite, contains Na and Mg as important constituents, dominated in the first-formed fumaroles, but now, 41 years after the eruption of Eldfell, is only a minor phase. The new mineral is named after the Icelandic volcanologist Niels Oskarsson.