Silver-bearing zinc-iron tetrahedrite-tennantite and freibergit fahlores approximating the simplified formula (Ag,Cu)10(Fe,Zn)2(As,Sb)4S13 have been equilibrated with excess electrum (AuxAg1−x) and chalcopyrite + pyrite + iron-bearing sphalerite (CuFeS2 + FeS2 + Fe0.05Zn0.95S) in evacuated silica tubes at 300 °C, in reversed silver-copper exchange experiments with less than 0.1 mg NH4Cl added as a transport medium. A thermodynamic formulation and parameters describing As-Ag incompatibility at 400 °C (Ebel and Sack, 1989), which incorporate large temperature dependencies of standard-state properties and composition-ordering systematics, are shown to apply equally well to these 300 °C results. A generalised graphical model for this mineral assemblage is presented, describing fahlore composition as a function of temperature and the compositions of coexisting electrum and (Fe,Zn)S, which define the Ag(Cu)−1 and Fe(Zn)−1 exchange properties controlling fahlore compositions.

Daliranite, ideally PbHgAs2S6, a new sulphosalt from the Zarshouran Au-As deposit, Takab region, Iran, occurs as a rare sulphosalt species at the Carlin-type Zarshouran Au-As deposit North of the town of Takab in the Province of West Azarbaijan, Iran. The new species is associated with orpiment, rarely with galkhaite, hutchinsonite and cinnabar. The strongly silicified matrix of the specimens has veinlets of sphalerite, with rare inclusions of galena and various (Cu)-Pb-As(Sb) sulphosalts. Daliranite occurs as matted nests of acicular and flexible fibres up to 200 μm in length and a width less than a few μm. The colour is orange-red with a pale orange-red streak and the lustre is adamantine. The mineral is transparent and does not fluoresce. The Mohs hardness is <2. Electron microprobe analyses give the empirical formula Pb0.95Tl0.01Hg1.04As2.10S5.91, ideally PbHgAs2S6, a new sulphosalt from the Zarshouran Au-As deposit, Takab region, Iran; the calculated density is 5.93 g cm–3. Unit-cell parameters were determined by an electron-diffraction study and refined from X-ray powder data. Daliranite is monoclinic primitive with a = 19.113(5) Å, b = 4.233(2) Å, c = 22.958(8) Å, β = 114.78(5)°, V = 1686.4 Å3 and Z = 8, a:b:c = 4.515:1:5.424, space group P2, Pm or P2/m. The strongest X-ray powder-diffraction lines [d in Å, (I), (hkl)] are: 8.676, (80), (200); 4.654, (50), (401); 3.870, (40), (211); 3.394, (50), (113); 3.148, (40b), (602); 2.892, (50), (600); 2.724, (100), (703); 2.185, (50), (319). The formula shows a sulphur excess which may correspond to S—S bonding (persulphide). The new sulphosalt is a late phase in the crystallization sequence, and was formed after orpiment, contemporaneously with quartz II, at a temperature between 157 and 193°C. The name honours Dr Farahnaz Daliran (University of Karlsruhe, Germany) in recognition of her outstanding contributions to research on ore deposits, especially Au, Zn and Fe, in Iran.

Coiraite, ideally (Pb,Sn2+)12.5As3Fe2+Sn4+S28, occurs as an economically important tin ore in the large Ag-Sn-Zn polymetallic Pirquitas deposit, Jujuy Province, NW-Argentina. The new mineral species is the As derivative of franckeite and belongs to the cylindrite group of complex Pb sulphosalts with incommensurate composite-layered structures. It is a primary mineral, frequently found in colloform textures, and formed from hydrothermal solutions at low temperature. Associated minerals are franckeite, cylindrite, pyrite-marcasite, as well as minor amounts of hocartite, Ag-rich rhodostannite. arsenopyrite and galena. Laminae of coiraite consist of extremely thin bent platy crystals up to 50 urn long. Electron microprobe analysis (n = 31) gave an empirical formula Pb11.21As2.99Ag0.13Fe1.10Sn6.13S28.0 close to the ideal formula (Pb11.3Sn2+1.2)Σ=12.5As3Fe2+Sn4+S28. Coiraite has two monoclinic sub-cells, Q (pseudotetragonal) and H (pseudohexagonal). Q: a 5.84(1) Å, b 5.86(1) Å, c 17.32(1) Å, β 94.14(1)°, F 590.05(3) Å3, Z = 4, a:b:c = 0.997:1:2.955; H (orthogonal setting): a 6.28(1) Å, b 3.66(1) Å, c 17.33(1) Å, β 91.46(1)°, V398.01(6) Å3, Z = 2, a∶b∶c = 1.716∶1∶4.735. The strongest Debye-Scherrer camera X-ray powder-diffraction lines [d in Å, (I), (hkl)] are: 5.78, (20), (Q and H 003); 4.34, (40), (Q 004); 3.46, (30), (Q and H 005); 3.339, (20), (Q 104); 2.876, (100), (Q and H 006); 2.068, (60), (Q 220).

The crystal structure of the rare mineral dalnegroite, Tl5−xPb2x(As,Sb)21−xS34 with x ≈ 1, was determined for a crystal from Lengenbach, Binn Valley, Switzerland. The structure is triclinic, space group P1, with a = 16.218(3), b = 42.546(7), c = 8.558(1) Å , α = 95.70(4), β = 90.18(3), γ = 96.38(4)°, V = 5838.9(9) Å3, Z = 4. Refinement of an isotropic model led to an R1 index of 0.0536 for 22226 observed reflections and 980 parameters, and R1 = 0.0590 for all 25266 independent reflections. Although dalnegroite cannot be considered a layered compound, its structure can be usefully described as a regular alternation of two kinds of layers stacked along the b axis, with four layers in the unit cell: (1) a layer 7.8 Å thick, at y ≈ 0.15 and 0.65, can be considered as derived from the SnS archetype; (2) a layer 13.6 Å thick, at y ≈ 0.35 and 0.85, derived from the PbS archetype. Different chemical compositions, such as Tl:Pb and Sb:As ratios, for different samples belonging to the chabournéite-dalnegroite family could play a central role in controlling different degrees of order, leading to different superstructures.

Dalnegroite, ideally Tl4Pb2(As12Sb8)Σ20S34, is a new mineral from Lengenbach, Binntal, Switzerland. It occurs as anhedral to subhedral grains up to 200 μm across, closely associated with realgar, pyrite, Sb-rich seligmanite in a gangue of dolomite. Dalnegroite is opaque with a submetallic lustre and shows a brownish-red streak. It is brittle; the Vickers hardness (VHN25) is 87 kg mm-2 (range: 69—101) (Mohs hardness ∼3—3½). In reflected light, dalnegroite is highly bireflectant and weakly pleochroic, from white to a slightly greenish-grey. In cross-polarized light, it is highly anisotropic with bluish to green rotation tints and red internal reflections.

According to chemical and X-ray diffraction data, dalnegroite appears to be isotypic with chabournéite, Tl5-xPb2x(Sb,As)21-xS34. It is triclinic, probable space group P1, with a = 16.217(7) Å, b = 42.544(9) Å, c = 8.557(4) Å, α = 95.72(4)°, β = 90.25(4)°, γ = 96.78(4)°, V = 5832(4) Å3, Z = 4.

The nine strongest powder-diffraction lines [d(Å) (I/I0) (hkl)] are: 3.927 (100) ( 10 0); 3.775 (45) (22); 3.685 (45) (60); 3.620 (50) (440); 3.124 (50) (2); 2.929 (60) (42); 2.850 (70) (42); 2.579 (45) (0 2); 2.097 (60) (024). The mean of 11 electron microprobe analyses gave elemental concentrations as follows: Pb 10.09(1) wt.%, Tl 20.36(1), Sb 23.95(1), As 21.33(8), S 26.16(8), totalling 101.95 wt.%, corresponding to Tl4.15Pb2.03(As11.86Sb8.20)S34. The new mineral is named for Alberto Dal Negro, Professor in Mineralogy and Crystallography at the University of Padova since 1976.

Reversed brackets on As and Sb partitioning between tetrahedrite-tennantite fahlores {∼CU10(Fe,Zn)2(Sb,As)4S13} and bournonite-seligmannite solid solutions {CuPb(Sb,As)S3} (400°C evacuated silica tubes, NH4Cl flux) indicate that the maximum nonidealities associated with the As-Sb substitution are about 165 (bournonite) and 250 (fahlore) cal/gfw on a per atom exchange basis. The experimental constraints are consistent with the following calibration of the As-Sb exchange reaction between these phases:

where kcal/gfw, X2 = Zn/(Zn + Fe) (or one-half the number of Zn atoms/formula unit) and X3 = As/(As + Sb) refer to atomic ratios in fahlore, and ΔG°23 = ΔH°23 = 2.59 ± 0.14 kcal/gfw (Raabe and Sack, 1984; Sack and Loucks, 1975; O'Leary and Sack, 1987; Sack, 1992).