Fe-Zn exchange reaction between tetrahedrite and sphalerite in natural environments

Microprobe and fluid inclusion analyses of hydrothermal ore deposits containing the subassemblage sphalerite+ tetrahedrite-tennantite [(Cu, Ag)₁₀(Fe, Zn)₂(As,Sb)₄S₁₃] reveal that the Gibbs energies of the reciprocal reaction Cu₁₀Zn₂Sb₄S₁₃ + Cu₁₀Fe₂As₄S₁₃ = Cu₁₀Fe₂Sb₄S₁₃ + Cu₁₀Zn₂As₄S₁₃ and the Fe-Zn exchange reaction 1/2Cu₁₀Fe₂Sb₄S₁₃ + ZnS = 1/2Cu₁₀Zn₂Sb₄S₁₃ + FeS are within the uncertainties of the values established by Sack and Loucks (1985) and Raabe and Sack (1984), 2.59±0.14 and 2.07±0.07 kcal/gfw. However, this study suggests that the Fe-Zn exchange reaction between sphalerite and Sb and Ag-rich tetrahedrites does not obey the simple systematics suggested by Sack and Loucks (1985) wherein tetrahedrite is assumed to behave as an ideal reciprocal solution. Instead these studies show that the configurational Gibbs energy of this exchange reaction,RTln[(X _Fe/X _Zn)^TET(X _ZnS/X _FeS)^SPH], corrected for sphalerite nonideality exhibits both a local maximum and minimum as a function of Ag/(Cu+Ag) ratio at a givenX _FeS ^SPH and temperature. The local maximum forX _FeS ^SPH 0.10 corresponds to the position of the cell edge maximum established for natural tetrahedrites by Riley (1974), Ag/(Ag+Cu)0.4. These studies and the results of structural refinements of Ag-bearing tetrahedrites suggest that in low silver tetrahedrites Ag is preferentially incorporated in trigonal-planar sites but that in tetrahedrites with intermediate and greater Ag/(Ag+Cu) ratio, Ag is preferentially incorporated in tetrahedral sites. A nonconvergent site ordering model for tetrahedrite is developed to quantify and extrapolate these predictions.     

Some electrical properties of fahlore Cu10(Zn,Fe)2(As,Sb)4S13

Natural Zn-tennantite Cu_10.10Ag_0.04(Zn_1.29-Fe_0.67)_1.96(As_3.04Sb_0.89)_3.93S_12.98 from Beresovskoe, Urals, behaves as an ordinary semiconductor in the temperature range 300–400 K and frequency range 10⁸–2.8·10¹⁰ Hz, and no ionic component conductivity is observed. This contrasts with the behaviour of synthetic tetrahedrites (both Cu-rich and Cu-poor) which are solid electrolytes. These results can be related to the number of vacancies per formula unit and the substitution scheme for the divalent metals in fahlore.     

Investigation into the nature of copper and silver sites in argentian tetrahedrites using EXAFS spectroscopy

Synchrotron radiation has been used to collect Cu K-edge and Ag K-edge EXAFS from several tetrahedrite, (Cu,Ag)₁₀(Zn,Fe,Cu)₂Sb₄S₁₃, minerals. The results have been used to investigate the coordination environment of the Ag and Cu, and to determine which sites in the structure are occupied by silver atoms when they replace copper. The Ag EXAFS spectrum of a sample with high silver content reveals an interaction between silver and antimony which may explain the anomalous decrease in unit cell size found in natural tetrahedrites when the silver content increases beyond four atoms per unit formula.     

Oxidation state and electronic configuration determination of copper in tetrahedrite group minerals by L-edge X-ray absorption spectroscopy

L-edge X-ray absorption spectroscopy employing a synchrotron radiation source has been used to study the electronic structure and valency of Cu in the chemically and structurally complex tetrahedrite group of minerals. Mechanical mixtures of Cu²⁺O and Cu⁺FeS₂ were used to estimate the relative cross sections of Cu²⁺ and Cu⁺; the absorption of Cu²⁺ at 931 eV is 25 times greater than that of Cu⁺ at 945 eV. Using this calibration, Cu²⁺/Cu ratios were found to vary from 0.00 to 0.054 in the tetrahedrite samples studied; the highest proportion of Cu²⁺ occurs in synthetic tetrahedrites with a composition close to Cu₁₂Sb₄S₁₃. This study reveals the utility of the technique for determining the valence state of copper in complex minerals, allowing the crystal chemistry to be more fully characterised.     

The role of Fe2+ and Fe3+ in synthetic Fe-substituted tetrahedrite

Summary Tetrahedrites with the composition between Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ were synthesized at 457 °C and 500 °C from the elements and carefully studied by Mössbauer spectroscopy of⁵⁷Fe. Between Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ iron is predominantly ferric. Between Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ iron is predominantly ferrous and occupies the tetrahedral M1-sites.

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Zusammenfassung Die Rolle von Fe²⁺ und Fe³⁺ in synthetischen Tetraedriten mit Fe-Substitution Tetraedrite mit einer Zusammensetzung zwischen Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ wurden bei 457 °C und 500 °C aus den Elementen synthetisiert und sorgfdltig mit Mössbauer-Spektroskopie von⁵⁷Fe untersucht. Zwischen Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ ist Eisen überwiegend dreiwertig. Zwischen Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₁Fe₂Sb₄S₁₃ ist Eisen überwiegend zweiwertig und besetzt die tetraedrisch koordinierten M1-Plätze.

     

Fahlore thermochemistry: Gaps inside the (Cu,Ag)<Subscript>10</Subscript>(Fe,Zn)<Subscript>2</Subscript>(Sb,As)<Subscript>4</Subscript>S<Subscript>13</Subscript> cube

Possible topologies of miscibility gaps in arsenian (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores are examined. These topologies are based on a thermodynamic model for fahlores whose calibration has been verified for (Cu,Ag)₁₀(Fe,Zn)₂Sb₄S₁₃ fahlores, and conform with experimental constraints on the incompatibility between As and Ag in (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores, and with experimental and natural constraints on the incompatibility between As and Zn and the nonideality of the As for Sb substitution in Cu₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores. It is inferred that miscibility gaps in (Cu,Ag)₁₀(Fe,Zn)₂As₄S₁₃ fahlores have critical temperatures several °C below those established for their Sb counterparts (170 to 185°C). Depending on the structural role of Ag in arsenian fahlores, critical temperatures for (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlores may vary from comparable to those inferred for (Cu,Ag)₁₀(Fe,Zn)₂As₄S₁₃ fahlores, if the As for Sb substitution stabilizes Ag in tetrahedral metal sites, to temperatures approaching 370°C, if the As for Sb substitution results in an increase in the site preference of Ag for trigonal-planar metal sites. The latter topology is more likely based on comparison of calculated miscibility gaps with compositions of fahlores from nature exhibiting the greatest departure from the Cu₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ and (Cu,Ag)₁₀(Fe,Zn)₂Sb₄S₁₃ planes of the (Cu,Ag)₁₀(Fe,Zn)₂(Sb,As)₄S₁₃ fahlore cube.     

Germanium-bearing Colusite in Siliceous Black Ore from the Ezuri Kuroko Deposit, Hokuroku District, Japan

Abstract. Germanium‐bearing colusite occurs with sphalerite, galena, tetrahedrite‐tennantite, chalcopyrite and pyrite in microdruses and veinlets in the siliceous black ore from the Ezuri Kuroko deposit in the Hokuroku district of Japan. X‐ray microdiffractometry of this mineral gives strongest lines at 1.60, 1.32 and 1.09 Å, which are consistent with the known powder diffraction data of colusite. On the basis of 32 S atoms per formula unit, electron microprobe analyses yield empirical chemical formulae of (Cu_{24 0}Fe_0.3Zn_1.0)_σ25.3V_1.9(A_s4.8Sb_0.2)_σ5.0Ge _1.3S₃₂ for Ge‐bearing colusite in close association with sphalerite, and (Cu_24.6Fe_0.9)_σ25.4V_1.8(A_s4.1 Sb_0.2)_σ4.3Ge_1.7S₃₂ for that coexisting with chalcopyrite, consistent with the ideal formula of Cu_24+xV₂(As, Sb)_6‐x(Sn, Ge)_xS₃₂ (x = 0 to 2) proposed by Spry et al. (1994) for this mineral species. The Ge‐bearing colusite mineralization is suggested to have occurred concurrently with consolidation of the siliceous black ore, possibly during hydrothermal modification in association with the igneous activity of the Ohtaki quartz diorite of the later Onnagawa stage. It is likely that biogenic siliceous ooze, a possible precursor of the siliceous black ore, may have served as an in situ source of Ge as well as other essential rare elements, leading to the formation of Ge‐bearing colusite during transformation or recrystallization of biogenic opal into a‐quartz.     

The tetrahedrite-freibergite series,with reference to the Mount Isa Pb-Zn-Ag orebody

Twenty eight electron microprobe analyses of freibergite from the Mount Isa (Queensland) Pb-Zn-Ag stratiform orebody, range in silver content from 18.4 to 42.5 wt. % Ag. These values significantly extend the tetrahedrite-freibergite series. The compositional range based on twenty-one complete analyses is indicated by the formula (Ag,Cu)_9.21–11.44(Fe,Zn)_1.59–2.31(Sb,As)_3.87–4.43S_13.0. As far as could be determined, Mount Isa freibergite is homogeneous and no marked compositional changes were detected either across individual grains, or in different grains of the same electron microprobe sample. The linear, atom for atom, replacement of copper by silver reported for lower silver bearing tetrahedrites continues in Mount Isa freibergite. A maximum silver content of about 51 wt. % Ag is predicted. X-ray investigations indicate however that in contrast to the structural expansion with increasing silver content reported for argentian tetrahedrite, Mount Isa freibergite contracts with increase in silver. The extrapolated lattice parameter for the theoretical freibergite (Ag₁₀(Fe,Zn)₂Sb₄S₁₃) end member is of the same order as tetrahedrite.     

The Hiendelaencina mining district (Guadalajara,Spain)

The Hiendelaencina mining district (Guadalajara, Spain), includes the ore deposits of the Hiendelaencina, La Bodera and Congostrina areas. In this paper a general overview of this district is given, with special emphasis on the parageneses, mineralizing stages and chemical characteristics of the sulphides and sulphosalts. These deposits contain silver in Sb-rich sulphosalts such as freibergite, pyrargyrite, polybasite, stephanite, freieslebenite and the Bi-rich sulphosalt, aramayoite. Three mineralizing stages have been detected in Hiendelaencina and Congostrina: (1) As-Fe; (2) Cu-Zn-Fe-Sb-Ag; and (3) Pb-Sb-Ag (±Bi) but only two in La Bodera (stages 2 and 3). The average sulphosalt formulas are: freibergite (Cu_0.5 Ag_5.9) (Fe_1.42 Zn_0.66) (Sb_4.49 As_0.02) S₁₃; pyrargyrite Ag_3.38 Sb_1.0 S₃; polybasite (Ag_16.3Cu_0.15) (Sb_2.8 As_0.15) S₁₁; stephanite Ag_6.7 Sb_1.38 S₄; freieslebenite Ag_1.1 Sb_0.83 Pb_1.05 S₃ and aramayoite Ag_1.06 Bi_{0. 35} Sb_0.7 Pb_0.03 S₂. The compositional patterns of these sulphosalts (mainly based on the Sb/(Sb + Ag), Ag/ (Ag + Cu), Sb(Ag + As) and Ag/(Ag + Cu) ratios) are outlined, pointing broadly to similar tendencies in their chemistry and genetic conditions.     

Two Se-bearing Ag–Bi Sulphosalts, Benjaminite and Matildite from the Ikuno Deposits, Hyogo Prefecture, Japan –Au–Ag Mineralization in Polymetallic Zone

Abstract: Se-bearing benjaminite and matildite are described from the polymetallic zone of the Ikuno deposits, Japan. The former is the first occurrence in Japan, and is from two separate veins, the Nanten and Daimaru, while the locality of the latter could not be specified. The empirical formulae of two benjaminites based on 22 atoms are (Ag_{2. 74}Cu_{0. 24})_{Σ2. 98}(Bi_{7. 00}Sb_{0. 01})_{Σ7. 01}(S_{10. 89}Se_{1. 12})_{Σ12. 01} (Nanten) and (Ag_{2. 90}Cu_{0. 10})_{Σ3. 00}(Bi_{6. 74}Pb_{0. 18}Sb_{0. 07})_{Σ6. 99}(S_{11. 68}Se_{0.33)Σ12. 01} (Daimaru), leading to the validation of the formula Ag₃Bi₇S₁₂ as the ideal one for benjaminite, and that of matildite based on 4 atoms is Ag_{1. 00}Bi_{1. 00}(S_{1. 78}Se_{0. 22})Σ_{2. 00}. These designate the substitution of Se for S in all of them, where Se is preferentially incorporated into these Ag-Bi sulphosalts. The unit-cell parameters of them and matildite are: a 13. 272, b 4. 037, c 20. 185 Å, and β 103. 16° (Daimaru), a 13. 270, b 4. 040, c 20. 273 Å, and β103. 17° (Nanten); and a 4. 0670, c 18. 996 Å, respectively. The products of Au-Ag mineralization in the Ikuno polymetallic vein-type deposits also occur as such Ag-Bi sulfosalts as benjaminite and matildite, in addition to pavonite, “treasurite derivative” and “electrum” with cassiterite in the polymetallic zone, and also do as “electrum”, acanthite, and pyrargyrite-proustite in the Au-Ag zone. The significant quantity of the Ag-Bi sulfosalts does not violate the zoning occupying the outermost part of the zonal distribution of ores in the deposits.     

Phase equilibrium study in the system Cu2S-PbS-Sb2S3: non-stoichiometry in sulfosalts and isothermal variation in sulfur fugacity

Evacuated silica tube experiments (+halide flux) were conducted in portions of the system Cu₂S-PbS-Sb₂S₃ at 440°C, using two-pyrrhotite indicator method to measure the sulfur fugacity. Product phases were identified by optical and X-ray powder diffraction methods supplemented with microprobe analyses. In addition to the previously reported mineral phases, famatinite (Cu₃SbS₄) appears to be a stable phase in the Sb₂S₃-rich portion of the system. Microprobe data indicate that almost all the sulfosalts depart from stoichiometry. Copper in Pb-Sb sulfosalts and Pb in chalcostibite and skinnerite are indicative of the coupled substitution 2Pb²⁺=Cu⁺+Sb³⁺. Pb-solubility in skinnerite and Cu-solubility in zinkenite are dependent on the initial bulk composition of the charges. The compositions of meneghinite and boulangerite compare well with their natural analogues. The maximum isothermal variation of logf _{s 2} falls in the range of-6.36 (1.06)logf _{s 2}11.12 (0.30). The experimentally derived logf _{s 2} values for some two phase assemblages, compare reasonably well with the respective minimum logf _{s 2} values calculated by the method of Craig and Barton (1973). The stable coexistence of famatinite with zinkenite plus stibnite instead of chalcostibite may be described by the sulfidation reaction: 3CuSbS₂+1/2 S₂=Cu₃SbS₄+Sb₂S₃.     

The distribution of Cu(II) and the magnetic properties of the synthetic analogue of tetrahedrite: Cu12Sb4S13

A wide investigation of the synthetic analogue of tetrahedrite, Cu₁₂Sb₄S₁₃, has been performed by a combination of several techniques, magnetisation and differential scanning calorimetric measurements, cw, and pulsed EPR spectroscopy, to obtain complementary information about the presence and the distribution of Cu(II). The high temperature susceptibility of the sample accounts for two Cu(II) per formula unit, in agreement with the charge balance. However, strong antiferromagnetic interactions, observed even at room temperature, are associated with a transition at 83(3) K. At lower temperatures a residual susceptibility is observed. At 4.2 K ESEEM experiments enabled observation of the chemical environment of the residual paramagnetic species. Cu(II) was found randomly distributed in the M(1) site. The statistical presence of nearest neighbouring Cu(II) ions justify the observed antiferromagnetic interactions and transition. Nevertheless, isolated paramagnetic ions have been determined below the Néel temperature: they are mainly located near the surface of the grains. A colour centre, previously observed in natural samples, has been also identified.     

New compositional and optical data for antimonian and bismuthian varieties of hemusite from Japan

Summary New compositional and optical data are reported for antimonian and antimonianbismuthian varieties of hemusite from epithermal Au-Ag-Cu deposits in Japan. The empirical formula for the antimonian variety, from the Iriki mine is: (Cu_5.83Fe_0.14Ag_0.01)_5.98Mo_1.03(Sn_0.54Sb_0.41Te_0.03Bi_0.02)_1.00(S_7.85Se_0.15)_8.00, and that of the Sb-Bi variety from the Kawazu mine is: (Cu_5.84Fe_0.14Ag_0.01)_5.99Mo_1.03(Sn_0.82Sb_0.11Bi_0.l0Te_0.04)_1.07(S_7.80Se_0.12)_7.92. The theoretical formula of hemusite is Cu⁺ ₄Cu²⁺ ₂MO⁴⁺Sn⁴⁺S₈, whilst the most probable formula of the Iriki hemusite is Cu⁺ _4.5CU²⁺ _1.5Mo⁴⁺Sn⁴⁺ _0.5Sb⁵⁺ _0.5S₈, with Sb⁵⁺ substituting for Sn⁴⁺ and forming (SbS₄)^3– tetrahedra as might be expected, given that the metal to sulphur ratio is 1, and given the sphalerite-like structure of the mineral. However Bi³⁺ cannot be so accommodated, resulting in a deficiency in (S + Se) for Kawazu hemusite. Reflectance spectra for both are compared with those of the tungsten analogue (compositional) of hemusite, kiddcreekite. The relationship between hemusitesensu stricto and these newly reported varieties is discussed in terms of simple and coupled chemical substitutions, and inferences are drawn on the valency of Sb, Bi, Mo and Cu in the hemusite structure.

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Neue chemische und optische Daten für antimon- und bismuthführende Varietäten von Hemusit aus Japan

Zusammenfassung Neue chemische und optische Daten für antimon- und bismuthführende Hemusite auf epithermalen Au-Ag-Cu Lagerstätten in Japan werden vorgelegt. Die empirische Formel für die antimon-führende Varietät aus der Iriki-Mine ist: (Cu_5.83Fe_0.14Ag_0.01)_5.98Mo_1.03(Sn_0.54Sb_0.41Te_0.03Bi_0.02)_1.00 (S_7.85Se_0.15)_8.00, und die der Sb-Bi Varietät aus der Kawazu Mine ist: (Cu_5.84Fe_0.14Ag_0.01)_5.99M0_1.03(Sn_0.82Sb_0.11Bi_0.l0Te_0.04)_1.07 (S_7.80Se_0.12)_7.92. Die theoretische Formel von Hemusit ist Cu⁺ ₄Cu²⁺ ₂Mo⁴⁺Sn⁴⁺S₈, während die wahrscheinlichere Formel für den Hemusit von Iriki Cu⁺ ₄Cu²⁺ _1.5Mo⁴⁺Sn⁴⁺ _0.5Sb⁵⁺ _0.5S₈, mit Sb⁵⁺ an der Stelle von Sn⁴⁺, das(SbS₄)^3– Tetraeder bildet, wie zu erwarten ist, unter der Voraussetzung, da das Metall zu Schwefelverhältnis 1 und die Struktur sphaleritähnlich ist. Bi³⁺ kann jedoch nicht in dieser Weise untergebracht werden, und das führt zu einem Mangel an (S + Se) für den Hemusit von Kawazu. Die Reflektions-Spektren beider Minerale werden mit denen des Wolfram-Equivalents von Hemusit (Kiddcreekit) verglichen. Die Beziehung zwischen Hemusitsensu stricto und diesen jetzt beschriebenen Varietäten wird auf der Basis einfacher und gekoppelter chemischer Substitution diskutiert. Auf dieser Basis werden Schlüsse auf die Valenz von Sb, Bi Mo und Cu in der Hemusit-Struktur gezogen.

     

Structure cristalline d'une ménéghinite naturelle pauvre en cuivre,Cu0,58Pb12,72(Sb7,04Bi0,24)S24Crystal structure of a Cu-poor natural meneghinite,Cu0.58Pb12.72(Sb7.04Bi0.24)S24

Cu-poor meneghinite from La Lauzière Massif (Savoy, France) has the composition (electron microprobe) (in wt%): Pb 59.50, Sb 20.33, Bi 1.19, Cu 0.87, Ag 0.05, Fe 0.03, S 17.62, Se 0.05, Total 99.64. Its crystal structure (X-ray on a single crystal) was solved with R1=0.0506, wR2=0.1026, with an orthorhombic symmetry, space group Pnma, and a=24.080(5) Å, b=4.1276(8) Å, c=11.369(2) Å, V=1130.0(4) Å³, Z=4. Relatively to the model of Euler and Hellner (1960), this structure shows a significantly lower site occupancy factor for the tetrahedral Cu site (0.146 against 0.25). Among the five other metallic sites, Bi appears in the one with predominant Sb. Developed structural formula: Cu_0.15Pb₂(Pb_0.53Sb_0.47)(Pb_0.46Sb_0.54)(Sb_0.75Pb_0.19Bi_0.06)S₆; the reduced one: Cu_0.58Pb_12.72(Sb_7.04Bi_0.24)S₂₄. The formation of such a Cu-poor variety seems to be related to specific paragenetic conditions (absence of coexisting galena), or to crystallochemical constraints (minor Bi). To cite this article: Y. Moëlo et al., C. R. Geoscience 334 (2002) 529–536.     

Calculation of the energetics for the oxidation of Sb(III) sulfides by elemental S and polysulfides in aqueous solution

Recent experimental studies have reported the existence of two new Sb sulfide species, Sb₂S₅²⁻ and Sb₂S₆²⁻, in alkaline sulfidic solutions in equilibrium with stibnite, Sb₂S₃, and orthorhombic S. These species contain Sb(V), which has also recently been identified in similar solutions using EXAFS by other researchers. This represents a significant change from the consensus a decade ago that sulfidic solutions of Sb contained only Sb(III) species. I have calculated from first principles of quantum mechanics the energetics for the oxidation of the Sb(III) sulfide dimer Sb₂S₄²⁻ to the mixed Sb(III,V) dimer Sb₂S₅²⁻ and then to the all Sb(V) dimer, Sb₂S₆²⁻. Gas-phase reaction energies have been evaluated using polarized valence double zeta effective core potential basis sets and Moller-Plesset second order treatments of electron correlation. All translational, rotational and vibrational contributions to the gas-phase reaction free energy have been calculated. Hydration energies have been obtained using the COSMO version of the self-consistent reaction field polarizable continuum method. Negative free energy changes are calculated for the oxidation of the dianion of the III,III dimer to the III,V dimer by both small polysulfides, like S₄H⁻, and elemental S, modeled as S₈. For the further oxidation of the III,V dimer to the V,V dimer the reaction free energies are calculated to be close to zero. The partially protonated Sb III,III dimer monoanion HSb₂S₄⁻ can also be oxidized, but the reaction is not so favorable as for the dianion. Comparison of the calculated aqueous deprotonation energies of H₂Sb₂S₄, H₂Sb₂S₅ and H₂Sb₂S₆ and their dianions with values calculated for various oxyacids indicates that the III,V and V,V dimers will have pK_a2 values <5, so that their dianions will be the dominant species in alkaline solutions. These results are thus consistent with the recent identification of Sb₂S₅²⁻ and Sb₂S₆²⁻ species. I have also calculated the Raman spectra of Sb₂S₅²⁻ and Sb₂S₆²⁻ to assist in their identification. The calculated vibrational frequencies of the III,V and V,V dimers are characteristically higher than those of the III,III dimer I previously studied. The III,V dimer may contribute shoulders to the Raman spectrum.     

The role of iron in tetrahedrite and tennantite determined by Rietveld refinement of neutron powder diffraction data

Rietveld refinement of neutron powder diffraction data on four samples of synthetic, iron-bearing tetrahedrite (Cu_12?xFe_xSb₄S₁₃) with x = 0.28, 0.69, 0.91, 2.19 and four samples of synthetic tennantite (Cu_12?xFe_xAs₄S₁₃) with x = 0.33, 0.38, 0.86, 1.5 indicate unambiguously that iron is incorporated into tetrahedral M1 (12d) sites and not into triangular M2 (12e) sites in the cubic crystal structure (space group I $ \ifmmode\expandafter\bar\else\expandafter\=\fi{4} Rietveld refinement of neutron powder diffraction data on four samples of synthetic, iron-bearing tetrahedrite (Cu_12−xFe_xSb₄S₁₃) with x = 0.28, 0.69, 0.91, 2.19 and four samples of synthetic tennantite (Cu_12−xFe_xAs₄S₁₃) with x = 0.33, 0.38, 0.86, 1.5 indicate unambiguously that iron is incorporated into tetrahedral M1 (12d) sites and not into triangular M2 (12e) sites in the cubic crystal structure (space group I 3 m). The refinement results also confirm that M2 is a split (24g), flat-pyramidal site situated statistically on both sides of the S1−S1–S2 triangle. In tetrahedrite, this split is about 0.6 ?, in tennantite about 0.7 ?. Trends in bond lengths and magnitude of the M2 split were evaluated by means of linear regression with Fe concentration as the independent variable.     

Mineralogy and textural relationships among sulphosalts and related minerals in the Bleikvassli Zn-Pb-(Cu) deposit, Nordland, Norway

Several distinct assemblages of Pb-Sb, Pb-As, Cu-Pb-Sb and Cu-Fe-Zn-Sn sulphosalts are identified in sulphide samples from Bleikvassli mine, Norway. Detailed optical microscopy and electron probe microanalysis have permitted investigation of textural relationships between minerals and compositional variations between different ore types. Tetrahedrite, typically containing 10–16?wt.% Ag (rare freibergite containing 25–30?wt.% Ag has also been identified in two samples), stannite (Cu₂(Fe>Zn)SnS₄), and meneghinite, CuPb₁₃Sb₇S₂₄, are widely distributed as trace constituents throughout massive pyritic and galena-rich ores. Native antimony and pyrargyrite occur in trace amounts in all ore types, as the breakdown products of earlier sulphosalts. Several distinct types of wall-rock mineralisation are present at Bleikvassli. Of considerable mineralogical interest are the coarse-grained sulphide mobilisates within the wall rock which contain a distinct?and characteristic suite of Pb-As sulphosalts:?tennantite?+?jordanite (Pb₁₄As₆S₂₃)?+?seligmannite (CuPbAsS₃) ± dufrenoysite (Pb₂As₂S₅). Bournonite (CuPbSbS₃) is the only Sb-bearing sulphosalt recognised in significant amounts within the mobilisates, meneghinite and tetrahedrite being conspicuously absent. These mobilisates display considerable Au enrichment; electrum can be confirmed, intimately associated with jordanite and tennantite. Appreciable Sb (up to 3?wt.%) is contained within galena in the mobilisates, in contrast to galena from massive ores which contains only negligible Sb. Contents of Ag and Bi in galena vary considerably in all ore types, but confirm earlier suggestions that galena is a major Ag-carrier at Bleikvassli. Boulangerite (Pb₅Sb₄S₁₁), jamesonite (FePb₄Sb₆S₁₄) and gudmundite (FeSbS) occur in trace amounts. Sn-sulphosalts are represented by kësterite, (Cu₂(Zn> Fe)SnS₄), but commonly zoned with respect to Zn/Fe ratio, in the mobilisates, rather than by stannite. A rare type of mobilisate, also in the wall rock, in which chalcocite and bornite are the main minerals, contains native Ag, stromeyerite (AgCuS), mckinstryite ((Ag,Cu)₂?S), Ag-free tetrahedrite, an unnamed Cu-Ag-Fe sulphide (Cu₃Ag₂FeS₄) and native Bi, myrmekitically intergrown with chalcocite. Although a comprehensive genetic model for the wall-rock mineralisation at Bleikvassli is largely impossible given the limitations in the present state of knowledge regarding mechanisms involved in remobilisation processes, a multi-stage model of remobilisation during regional metamorphism is considered to best explain the observations. An interplay of different solid- and liquid-state remobilisation mechanisms, in various combinations, is required to account for the macro- and microscopic observations. Remobilisation probably began during the earlier stages of metamorphism, with crystallisation and further remobilisation taking place during the entire metamorphic cycle, giving rise to the extensive chemical and mineralogical diversity observed today. Preserved mineral assemblages and their textural relationships reflect a complex sequence of replacement and decomposition reactions taking place during the latest phase of late-metamorphic crystallisation and subsequent cooling.     

Chemistry of some Pb-(Cu,Fe)-(Sb,Bi sulfosalts from France and Portugal. Implications for the crystal chemistry of lead sulfosalts in the Cu-poor part of the Pb2S2-Cu2S-Sb2S3-Bi2-Bi2S3 system

Electron microprobe analysis of Pb-Cu(Fe)-Sb-Bi sulfosalts from Bazoges and Les Chalanches (France), and Pedra Luz (Portugal), give new data about (Bi, Sb) solid-solution and incorporation of the minor elements Cu, Fe or Ag in jaskolskiite, and in izoklakeite-giessenite and kobellite-tintinaite series. Jaskolskiite from Pedra Luz has high Sb contents (from 17.9 to 20.7 wt.%), leading to the extended general formula: Cu _x Pb_2+x (Sb_1–y Bi _y )_2–x S₅, with 0.10 x 0.22 and 0.19 y 0.41. Fe-free, Bi-rich izoklakeite from Bazoges has high Ag contents (up to 2.2 wt. %), leading to the simplified formula Cu₂Pb₂₂Ag₂(Bi, Sb)₂₂S₅₇; in Les Chalanches it contains less Ag content (1.2 wt.%), but has an excess of Cu that gives the formula: Cu_2.00 (Cu_0.49Ag_1.18)_=1.67Pb_22.70(Bi_12.63Sb_8.99)_=21.62S_57.27.In tintinaite from Pedra Luz, the variation of the Fe/Cu ratio can be explained by the substitution: Cu + (Bi, Sb) Fe + Pb; Fe-free kobellite from Les Chalanches has a Cu-excess, corresponding to the formula Cu_2.81Ag_0.54Pb_9.88(Bi_10.37Sb_5.21)_=15.38S_35.09. Eclarite from the type locality, structurally related to kobellite, shows a Cu excess too. In natural samples of the kobellite homologous series, Fe is positively correlated with Pb, and its contents never exceed that of Cu. Ag substitutes for Pb, together with (Bi, Sb). Taking into account the possibility of Cu excess, but excluding formal Cu²⁺ and Fe³⁺, general formulae can be written: