Physics and Chemistry of Minerals

, Volume 35, Issue 8, pp 455–465 | Cite as

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

  • Karen Friese
  • Andrzej Grzechnik
  • Emil MakovickyEmail author
  • Tonči Balić-Žunić
  • Sven Karup-Møller
Original Paper


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.


Tetrahedrite Tennantite Iron substitution Rietveld refinement Crystal structure at 25 and 250°C Split trigonal planar copper positions 



The synchrotron experiments were carried out during the beamtime HS-2693; the experimental assistance from the staff of the Swiss–Norwegian Beamlines at ESRF is gratefully acknowledged. EM, SKM, and TBŽ have been supported by the grant no. 21–03–0519 of the State Research Council for Nature and Universe (Denmark). AG and KF acknowledge support by the European Mineral Science Initiative (EuroMinSci/Eurocore) of the European Science Foundation as well as the additional financial support from the Ministerio de Ciencia y Tecnología (Spain) and the Gobierno Vasco. Helpful reviews by Prof. F. di Benedetto and Prof. R.R. Gainov are gratefully acknowledged.


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Copyright information

© Springer-Verlag 2008

Authors and Affiliations

  • Karen Friese
    • 1
  • Andrzej Grzechnik
    • 1
  • Emil Makovicky
    • 2
    Email author
  • Tonči Balić-Žunić
    • 2
  • Sven Karup-Møller
    • 3
  1. 1.Departamento de Física de la Materia CondensadaUniversidad del País VascoBilbaoSpain
  2. 2.Department of Geography and GeologyUniversity of CopenhagenCopenhagenDenmark
  3. 3.Institute for Environment and ResourcesDanish Technical UniversityLyngbyDenmark

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