Pirquitasite, ideally Ag2ZnSnS4 (disilver zinc tin tetra­sulfide), exhibits tetra­gonal symmetry and is a member of the stannite group that has the general formula A2BCX 4, with A = Ag, Cu; B = Zn, Cd, Fe, Cu, Hg; C = Sn, Ge, Sb, As; and X = S, Se. In this study, single-crystal X-ray diffraction data are used to determine the structure of pirquitasite from a twinned crystal from the type locality, the Pirquitas deposit, Jujuy Province, Argentina, with anisotropic displacement parameters for all atoms, and a measured composition of (Ag1.87Cu0.13)(Zn0.61Fe0.36Cd0.03)SnS4. One Ag atom is located on Wyckoff site Wyckoff 2a (symmetry -4..), the other Ag atom is statistically disordered with minor amounts of Cu and is located on 2c (-4..), the (Zn, Fe, Cd) site on 2d (-4..), Sn on 2b (-4..), and S on general site 8g. This is the first determination of the crystal structure of pirquitasite, and our data indicate that the space group of pirquitasite is I-4, rather than I-42m as previously suggested. The structure was refined under consideration of twinning by inversion [twin ratio of the components 0.91 (6):0.09 (6)].

A new mineral species, fluorlamprophyllite (IMA2013-102), ideally Na3(SrNa)Ti3(Si2O7)2O2F2, has been found in the Poços de Caldas alkaline massif, Morro do Serrote, Minas Gerais, Brazil. Alternatively, the idealized chemical formula could be written as (SrNa)[(Na3Ti)F2][Ti2(Si2O7)2O2], setting the large interlayer cations before the cations of the layer. Fluorlamprophyllite is the F-analogue of lamprophyllite. It is associated with aegirine, analcime, natrolite, nepheline and microcline. Fluorlamprophyllite crystals are brownish-orange and bladed. The mineral is transparent with a pale yellow streak and an adamantine lustre. It is brittle and has a Mohs hardness of ~3; cleavage is perfect on {100} and no parting was observed. The calculated density is 3.484 g/cm3. Optically, fluorlamprophyllite is biaxial (+), with α = 1.735(7), β = 1.749(7) and γ = 1.775(9) and 2Vmeas = 72(3)°. An electron microprobe analysis produced an average composition (wt.%) (9 points) of Na2O 10.63(30), K2O 0.47(3), SiO2 30.51(13), SrO 18.30(24), MgO 0.81(17), Al2O3 0.23(2), CaO 1.11(7), MnO 5.03(38), TiO2 27.41(87), Fe2O3 2.45(37), F 2.86(23), plus H2O 1.00 (added to bring the total close to 100%), –O = F –1.20, with the total = 98.61%. The elements Nb and Ba were sought, but contents were below microprobe detection limits. The resultant chemical formula was calculated on the basis of 18 (O + F) atoms per formula unit. The addition of 1.00 wt.% H2O brought [F+(OH)] = 2 pfu, yielding (Na2.63Sr1.35Mn0.54Ca0.15Mg0.15K0.08)Σ4.90(Ti2.63Fe0.24Al0.04)Σ2.91Si3.89O16[F1.15(OH)0.85]Σ2.00. The mineral is monoclinic, with space group C2/m and unit-cell parameters a = 19.255(2), b = 7.0715(7), c = 5.3807(6) Å, β = 96.794(2)° and V = 727.5(1) Å3. The structure is a layered silicate inasmuch as the O atoms are arranged in well-defined, though not necessarily close-packed layers.

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Natropalermoite, ideally Na2SrAl4(PO4)4(OH)4, the Na-analogue of palermoite, is a new mineral from the Palermo No. 1 mine, Groton, New Hampshire, USA. Associated minerals are palermoite, eosphorite and quartz. Natropalermoite crystal sare prismatic with striations parallel to the direction of elongation (the a axis) up to 200 μm × 50 μm × 45 μm in size. The mineral is colourless, transparent with a white streak and vitreous lustre and is visually indistinguishable from palermoite. It is brittle with subconchoidal fracture and has a Mohs hardness of 5.5. Cleavage is perfect on {001}, fair on {100} and no parting was observed. The calculated density is 3.502 g cm–3. Natropalermoite is biaxial (–), α = 1.624(1), β = 1.641(1), γ = 1.643(1) (589nm), 2Vmeas = 43(4)°, 2Vcalc = 38°. An electron microprobe analysis yielded an empirical formula (based on 20 O apfu) of (Na1.69Li0.31)∑2.00(Sr0.95Mg0.04Ca0.02Ba0.01)∑1.02(Al3.82Mn0.03Fe0.03)∑3.88(P1.01O4)4(OH)4.Natropalermoite is orthorhombic, space group Imcb, a = 11.4849(6), b = 16.2490(7), c = 7.2927(4) Å, V = 1360.95(17) Å3, Z = 4. Natropalermoite is isotypic with palermoite, but substitution of the larger Na for Li results in substantial increase of the b cell parameter. Four of the seven Na–O distances are longer than their equivalents in palermoite, resulting in a more regular 7-fold coordination polyhedron about Na. The eight strongest peaks in the calculated X-ray powder diffraction are [dcalc(Å),Irel%, (hkl)]: [3.128, 100, (321)], [4.907, 68, (121)], [3.327, 48, (022)], [4.689, 45, (220)], [3.078, 45, (202)], [2.453, 38, (242)], [2.636, 35, (411)], [2.174, 35, (422)].

The intergrowths and compositions of supergene copper sulfide minerals from drill hole MOR-4511 in the Western Copper area of the Morenci mine, Greenlee County, Arizona, have been examined by reflected light microscopy and electron probe microanalysis (EPMA) to better understand the formation of supergene sulfides with implications for hydrometallurgical processing. The supergene copper sulfides occur in three main textures: partial to complete replacement of chalcopyrite, partial replacement of pyrite, and partial to complete replacement of one another. Compositions of copper sulfides vary widely, but (CuþFe):S ratios of 1.80 6 0.05, 1.92 6 0.03, and 1.10 6 0.10 are dominant. No stoichiometric Cu 2 S was found. At shallower depths in the supergene blanket and near/within faults, high (CuþFe):S phases (with ratios of 1.80 6 0.05 and 1.92 6 0.03) replacing primary chalcopyrite and pyrite or lower (CuþFe):S supergene sulfides are dominant, and near the base of the blanket low (CuþFe):S phases (with ratios of 1.10 6 0.10) replacing primary chalcopyrite or higher (CuþFe):S supergene sulfides gradually become more dominant. This indicates high concentration of Fe 3þ , Fe 2þ , and Cu 2þ , necessary to form high (CuþFe):S phases, at shallower depths and near sources of unreacted fluid, such as faults. Formation of low (CuþFe):S phases directly from chalcopyrite or from high (CuþFe):S phases could be controlled by decreased concentrations of iron species and Cu 2þ due to reaction with primary chalcopyrite and pyrite as fluids descend or migrate away from faults, reduced access to supergene fluids, and/or lower pyrite-chalcopyrite ratios. The compositional patterns of supergene copper sulfide minerals observed at Morenci are similar to those observed in other supergene enrichment blankets of porphyry copper systems worldwide and are even more similar to compositions seen in leaching experiments of synthetic copper and copper-iron sulfides.