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.     

Crystal structures of iron bearing tetrahedrite and tennantite at 25 and 250°C by means of Rietveld refinement of synchrotron data

Rietveld refinement of X-ray synchrotron data was performed for two synthetic tetrahedrite samples, with 0.61 and 1.83 Fe atoms, and two synthetic tennantite samples with 0.10 and 1.23 Fe atoms p.f.u. M₁₂(Sb,As)₄S₁₃. Measurements were performed at 25 and 250°C. For both the phases, increased Fe substitution is reflected in the increased tetrahedral ‘Cu1’–S distance (‘Cu1’ is a site of Fe substitution) and Cu2–S distances. Cu2 was refined as a split position; the Cu2–Cu2 split about the plane of the S1₂S2 triangle is about 0.56 and 0.65 Å for tetrahedrite and tennantite, respectively. Cu2–Cu2 distances in the structure cavity are 2.8–2.9 Å. Between 25 and 250°C, the lattice parameter a increased by 0.02–0.04 Å and the interatomic distances by 0.01 Å on an average. Thermal expansion coefficients of little-substituted samples are similar to those of unsubstituted samples, whereas thermal expansion appears to decrease with increasing substitution by Fe. The Cu2–Cu2 split increases at 250°C by about 0.1 Å for tetrahedrite and by more than 0.15 Å for tennantite but the cage expansion is minimal so that the Cu2–Cu2 distances in the cavity decrease with temperature. Difference Fourier maps indicate that there is little residual electron density left between the two Cu2 half-sites in tetrahedrite but this inter-site density is substantially higher in tennantite. It increases with temperature, especially in the little-substituted tennantite sample.     

Copper valence,structural separation and lattice dynamics in tennantite (fahlore): NMR,NQR and SQUID studies

Electronic and magnetic properties of tennantite subfamily of tetrahedrite-group minerals have been studied by copper nuclear quadrupole resonance (NQR), nuclear magnetic resonance (NMR) and SQUID magnetometry methods. The temperature dependences of copper NQR frequencies and line-width, nuclear spin-lattice relaxation rate T ₁⁻¹ and nuclear spin-echo decay rate T ₂⁻¹ in tennantite samples in the temperature range 4.2–210 K is evidence of the presence of field fluctuations caused by electronic spins hopping between copper CuS₃ positions via S₂ bridging atom. The analysis of copper NQR data at low temperatures points to the magnetic phase transition near 65 K. The magnetic susceptibility in the range 2–300 K shows a Curie–Weiss behavior, which is mainly determined by Fe²⁺ paramagnetic substituting ions.