Towards the Recovery of By-Product Metals from Mine Wastes: An X-Ray Absorption Spectroscopy Study on the Binding State of Rhenium in Debris from a Centennial Iberian Pyrite Belt Mine


Rhenium is a very scarce element, occurring in the Earth's crust mainly carried by molybdenite (MoS2). Due to a very low availability comparative to actual industrial demand, rhenium is nowadays one of the most expensive mineral commodities and an increased interest is focused on ex- ploring residues resulting from a long-term mining, particularly of sulphide ore deposits. It is therefore noteworthy to assign the presence of rhenium (in a concentration up to 3 ppm) in the waste materials from the old sulphur factory at the abandoned mine of Sao Domingos (Iberian Pyrite Belt, Southeast Portugal), exploited since the Roman occupation of Iberia. Aiming at a potential sustainable recovery of rhenium as a by-product, X-ray near-edge absorption spectroscopy (XANES) was applied to clarify the Re-binding and mode of occurrence by comparing Re L3-edge XANES spectra obtained from mine waste samples (previously fully characterized by X-ray laboratory techniques) with similar spectra collected from Re-rich molybdenites (Mo1-xRexS2) and from Re-O model compounds configuring various valences and coordination environments of rhenium ions. Obtained results are commented, ruling out a possible Re-S binding and rather conforming with the binding of rhenium to oxygen in the analysed mine waste materials.

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Figueiredo, M. , Silva, T. , Veiga, J. , de Oliveira, D. and Batista, M. (2014) Towards the Recovery of By-Product Metals from Mine Wastes: An X-Ray Absorption Spectroscopy Study on the Binding State of Rhenium in Debris from a Centennial Iberian Pyrite Belt Mine. Journal of Minerals and Materials Characterization and Engineering, 2, 135-143. doi: 10.4236/jmmce.2014.22018.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Noddack, I. and Noddack, W. (1931) Die Geochemie des Rheniums. Zeitshrift für Physikalische Chemie, A154, 207-244.
[2] Fleischer, M. (1959) The Geochemistry of Rhenium, with Special Reference to Its Occurrence in Molybdenite. Economic Geology, 54, 1406-1413.
[3] Bernard, A., Symons, R.B. and Rose, W.I. (1990) Volatile Transport and Deposition of Mo, W and Re in High Temperature Magmatic Fluids. Applied Geochemistry, 5, 317-326.
[4] Ishihara, S. (1988) Rhenium Contents of Molybdenites in Granitoid-Series Rocks in Japan. Economic Geology, 83, 1047-1051.
[5] Berzina, A.N., Sotnikov, V.I., Economou-Eliopoulos, M. and Eliopoulos, D.G. (2005) Distribution of Re in Molybdenite from Porphyry Cu-Mo and Mo-Cu Deposits of Russia (Siberia) and Mongolia. Ore Geology Reviews, 26, 91-113.
[6] Voudouris, P.C., Melfos, V., Spry, P.G., Bindi, L., Kartal, T., Arikas, K., Moritz, R. and Ortelli, M. (2009) Rhenium-Rich Molybdenite and Rheniite in the Pagoni Rachi Mo-Cu-Te-Ag-Au Prospect, Northern Greece: Implications for the Re Geochemistry of Porphyry-Style Cu-Mo and Mo Mineralization. Canadian Mineralogist, 47, 1013-1036.
[7] Brown, M., Lazo, F., Carter, P., Goss, B. and Kirwin, D. (2010) The Geology and Discovery of Merlin Mo-Re Zone of Mount Dore Deposit, Mount Isa Inlier, NW Queensland, Australia. SGA News, 27, 9-15.
[8] Aminzadeh, B., Shahabpour, J. and Maghami, M. (2011) Variation of Rhenium Contents in Molybdenites from the Sar Cheshmeh Porphyry Cu-Mo Deposits in Iran. Resource Geology, 61, 290-295.
[9] Krebs, B., Müller, H. and Beyer, H. (1968) A New Type of Oxide Structure: The Crystal Structure of Rhenium (VII) Oxide. Chemical Communications (London), 61, 263-264.
[10] Amman, P.R. and Loose, T.A. (1972) Rhenium Volatilization during Molybdenite Roasting. Metallurgical Transactions, 3, 1020-1021.
[11] Korzhinsky, M.A., Tkachenko, S.I., Shmulovich, K.I., Taran, Y.A. and Steinberg, G.S. (1994) Discovery of a Pure Rhenium Mineral at Kudriavy Volcano. Nature, 369, 51-52.
[12] Kojonen, K.K., Roberts, A.C., Isom?ki, O.-P., Knauf, V.F., Johanson, I. and Pakkanen, L. (2004) Tarkianite, (Cu,Fe) (Re,Mo)4S8, a New Mineral Species from the Hitura Mine, Nivala, Finland. Canadian Mineralogist, 42, 539-544.
[13] Bare, S.R., Kelly, S.D., Vila, F.D., Boldingh, E., Karapetrova, E., Kas, J., Mickelson, G.E., Modika, F.S., Yang, N. and Rehr, J.J. (2011) Experimental (XAS, STEM, TPR and XPS) and Theoretical (DFT) Characterization of Supported Rhenium Catalysts. Journal of Physical Chemistry C, 115, 5740-5755.
[14] Naor, A., Eliaz, N., Gileadi, E. and Taylor, S.R. (2010) Properties and Applications of Rhenium and Its Alloys. AMMTIAC Quarterly, 5, 11-15.
[15] Batista, M.J., Matos, J.X., Figueiredo, M.O., de Oliveira, D., Silva, T.P., Santana, H. and Quental, L. (2011) Fingerprints for Mining Products and Wastes from the S. Domingos, Aljustrel and Neves Corvo Mines—A Sustainable Perspective. Proceedings of the VIII Iberian Congress of Geochemistry, Castelo-Branco, 6.
[16] Webb, J. (1958) Observations on the Geology and Origin of the S?o Domingos Pyrite Deposit, Portugal. Comunica??es dos Servi?os Geológicos de Portugal, 42, 119-143.
[17] Matos, J.X., Pereira, Z., Oliveira, V. and Oliveira, J.T. (2006) The Geological Setting of the S?o Domingos Pyrite Orebody, Iberian Pyrite Belt. Proceedings of the VII National Geology Congress, Estremoz, 283-286.
[18] Walker, T.L. (1911) Report on the Molybdenum Ores of Canada. Government Printing Bureau, Department of Mines, Ottawa, No. 93, 30-31.
[19] Witschek, G., Fröba, M., Füess, H. and Metz, W. (1994) XAS and XRD Studies of Rhenium-Oxygen Compounds. Fresenius Journal of Analytical Chemistry, 349, 230-231.
[20] Corá, F., Stachiotti, M.G., Catlow, C.R.A. and Rodriguez, C.O. (1997) Transition Metal Oxide Chemistry: Electronic Structure Study of WO3, ReO3 and NaWO3. Journal of Physical Chemistry B, 101, 3945-3952.
[21] Morrow, J.C. (1963) The Crystal Structure of KReO4. Acta Crystallographica, 13, 443.
[22] Mande, C., Pendharkar, A.V. and Chakravorti, M.C. (1972) The Shapes of L3 Absorption Discontinuity of Rhenium in Compounds. Proceedings of the Indian Academy of Sciences, Section A, 75, 209-216.
[23] Fr?ba, M., L?chte, K. and Metz, W. (1996) XANES Studies on Rhenium L Absorption Edges of Re2O7 Graphite Intercalation Compounds and Other Rhenium-Oxygen Compounds. Journal of Physical Chemistry of Solids, 57, 635- 641.
[24] Tougerti, A., Crystol, S., Briois, V., La Fontaine, C., Villain, F. and Joly, Y. (1996) XANES Study of Rhenium Oxide Compounds at the L1 and L3 Absorption Edges. Physical Review B, 57, 635-641.
[25] Cauchois, Y. and Mott, N.F. (1949) The Interpretation of X-Ray Absorption Spectra of Solids. Philosophical Magazine, 40, 1260-1269.
[26] Kuzmin, A., Purans, J., Benfatto, M. and Natoli, C.R. (1993) X-Ray Absorption Study of Rhenium L1 and L3 Edges in ReO3: A Multiple Scattering Approach. Physical Review B, 47, 2480-2486.
[27] Silva, T.P., Figueiredo, M.O., de Oliveira, D.P., Veiga, J.P. and Batista, M.J. (2013) Molybdenite as a Rhenium Carrier: First Results of a Spectroscopic Approach Using Synchrotron Radiation. Journal of Minerals and Materials Characterization and Engineering, 1, 207-211.
[28] Figueiredo, M.O., Silva, T.P., Batista, M.J., Veiga, J.P. and de Oliveira, D.P. (2013) Opportunities for Recovering Critical Raw Materials from Mine Wastes: The Type-Case of Rhenium in Residues from the Exploitation of Old Portuguese Mines. WASTES: Solutions, Treatments and Opportunities, 2nd International Conference, Braga/Portugal, September 2013, Poster, Book of Abstracts, 163-164.

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