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Rhenium in Molybdenite: a Database Approach to Identifying Geochemical Controls on the Distribution of a Critical Element

  • Isabel F. BartonEmail author
  • Christian A. Rathkopf
  • Mark D. Barton
Article
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Abstract

Molybdenite is the world’s principal source of rhenium (Re), a critical element in multiple high-tech applications. However, the Re contents in molybdenite vary by orders of magnitude on scales ranging from single grains to whole deposits. In order to better understand the systematics of this variation and what geochemical factors control molybdenite Re concentration, and hence overall Re resources, we examine global patterns in molybdenite Re contents through a compilation of > 3000 measurements of Re in molybdenite from > 700 mainly ore-bearing moderate- to high-temperature hydrothermal systems of different types. Our results are similar to but expand on those of earlier studies. Rhenium concentration in molybdenite has a lognormal distribution and varies systematically with type of geologic system, intrusive lithology, and Mo grade. The lowest-Re molybdenite occurs in greisens (geometric mean 1 ppm ± a multiplicative standard deviation of 9), quartz vein-hosted W-Sn deposits (2 ± 5 ppm), unmineralized granites and granodiorites (12 ± 8 ppm), intrusion-related deposits (24 ± 8 ppm), and porphyry W-Sn deposits (16 ± 11 ppm). Rhenium is most enriched in molybdenites from volcanic sublimates (23,800 ± 5 ppm), with skarn Fe and Au (560 ± 5 ppm and 540 ± 3 ppm respectively) and porphyry Cu and Cu-Au deposits next (470 ± 4 and 430 ± 7 ppm respectively). Among porphyries, skarns, and quartz vein-hosted deposits, Re is most highly concentrated in molybdenites from Cu and Au systems and its concentration decreases systematically through Cu-Mo, Mo, Sn, and W deposits. In nearly all cases, molybdenites from systems associated with intermediate igneous rocks contain more Re than molybdenites from systems of the same type with more felsic rock associations. The disparity between Re contents of molybdenite in felsic and intermediate systems is largest for porphyries, quartz vein-hosted, and skarn deposits and is near zero for subeconomic or barren granite and granodiorite Mo systems; felsic intrusion-related deposits have slightly higher molybdenite Re than their equivalents associated with intermediate intrusions. In most systems, molybdenite Re content does not correlate with metal grade, but may have an inverse correlation with Au grade in intrusion-related deposits (based on a small number of data points) and does exhibit a strong inverse correlation with deposit Mo grade. Dilution of Re through larger amounts (higher deposit grades) of molybdenite explains about 40% of this correlation, but the relative enrichment of Re in molybdenite from low-Mo deposits must also reflect some selective enrichment of Re/Mo in porphyry Cu systems compared to porphyry Mo systems. We found no evidence for secular increase or other systematic temporal variation in molybdenite Re content. The data regarding the use of molybdenite Re content as a proxy for mantle influence are ambiguous. Nearly all observed empirical correlations can be traced back to differences in redox state and sulfide concentration, the two geochemical factors identified here and by previous experimental work as the controlling influences on Re mobility under hydrothermal conditions. Hydrothermal systems with reducing conditions (W- and Sn-rich) tend to have low molybdenite Re even though compiled whole-rock data indicate that their source rocks have as much or more Re as those of more oxidized systems (e.g., Cu-rich). Vapor-phase exsolution, crustal assimilation, and mixing with external fluids may all enrich molybdenite Re concentrations in individual deposits and deposit types, but their extent and importance in overall hydrothermal concentration of Re is uncertain. Thus, it appears that the available molybdenite Re resource in an ore deposit largely depends on how the deposit’s redox and sulfidation conditions have varied over time and space during the timespan of hydrothermal activity. Oxidized, high-sulfide conditions tend to concentrate Re in molybdenite, whereas reducing conditions tend to leave Re dispersed at low concentrations in the bulk rock.

Keywords

rhenium molybdenite Re-Os porphyry deposits exploration rhenium behavior in hydrothermal systems 

Notes

Acknowledgments

This study was sponsored by Freeport-McMoRan Copper & Gold. In particular, we thank Richard Leveille, who suggested the project originally, along with Robert Jenkins and Ralph Stegen (all of Freeport-McMoRan) for their support, as well as for providing the Bagdad samples included in the database. We are also indebted to Eric Seedorff and Frank Mazdab (University of Arizona) for their advice on the study. David Selby, Panagiotis Voudouris, Jeff Mauk, and four anonymous reviewers provided helpful comments and suggestions.

Compliance with Ethical Standards

Conflict of Interest

The authors declare that they have no conflict of interest.

Supplementary material

42461_2019_145_MOESM1_ESM.xlsx (263 kb)
ESM 1. A. Excel spreadsheet database of > 3000 Re concentrations in molybdenite, with deposit type, metal grades, deposit ages, references, and sample and analytical types so far as could be determined. B. References to literature used in compilation of Re concentrations in database. (XLSX 262 kb)
42461_2019_145_MOESM2_ESM.docx (38 kb)
ESM 2 C. Explanation of the criteria and references used to assign classifications to deposits not clearly affiliated with one particular category. (DOCX 38 kb)

References

  1. 1.
    John DA, Seal RR II, Polyak DE (2017) Rhenium, Chap. P. In: Schulz KJ, DeYoung JH Jr, Seal RR II, Bradley DC (eds) Critical mineral resources of the United States—economic and environmental geology and prospects for future supply, vol 1802. U.S. Geological Survey Professional Paper, pp P1–P49Google Scholar
  2. 2.
    John D, Taylor R (2016) By-products of porphyry copper and molybdenum deposits. Rev Econ Geol 18:137–164Google Scholar
  3. 3.
    Rathkopf C, Mazdab F, Barton I, Barton MD (2017) Grain-scale and deposit-scale heterogeneity of Re distribution in molybdenite at the Bagdad porphyry Cu-Mo deposit, Arizona. J Geochemic Explor 178:45–54CrossRefGoogle Scholar
  4. 4.
    Giles D., and Schilling J., 1972: Variation in rhenium content of molybdenite. Proceedings of the 24th International Geological Congress 10: 145-152.Google Scholar
  5. 5.
    Terada K, Osaki S, Ishihara S, Kiba T (1971) Distribution of rhenium in molybdenites from Japan. Geochem J 4:123–141CrossRefGoogle Scholar
  6. 6.
    Newberry R (1979) Polytypism in molybdenite (II): relationships between polytypism, ore deposition/alteration stages and rhenium contents. Am Mineral 64:768–775Google Scholar
  7. 7.
    Berzina A, Sotnikov V, Economou-Eliopoulos M, Eliopoulos D (2005) Distribution of rhenium in molybdenite from porphyry Cu-Mo and Mo-Cu deposits of Russia (Siberia) and Mongolia. Ore Geol Rev 26:91–113CrossRefGoogle Scholar
  8. 8.
    Voudouris P, Melfos V, Spry PG, Bindi L, Moritz R, Ortelli M, Kartal T (2013) Extremely Re-rich molybdenite from porphyry Cu-Mo-Au prospects in northeastern Greece: mode of occurrence, causes of enrichment, and implications for gold exploration. Minerals 3:165–191CrossRefGoogle Scholar
  9. 9.
    Ciobanu C, Cook N, Kelson C, Guerin R, Kalleske N, Danyushevsky L (2013) Trace element heterogeneity in molybdenite fingerprints stages of mineralization. Chem Geol 347:175–189CrossRefGoogle Scholar
  10. 10.
    Coope JA (1973) Geochemical prospecting for porphyry copper-type mineralization—a review. J Geochem Explor 2:81–102CrossRefGoogle Scholar
  11. 11.
    Voudouris P, Melfos V, Spry P, Bindi L, Kartal T, Arikas K (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. Can Mineral 47:1013–1036CrossRefGoogle Scholar
  12. 12.
    Fleischer M (1959) The geochemistry of rhenium, with special reference to its occurrence in molybdenite. Econ Geol 54:1406–1413CrossRefGoogle Scholar
  13. 13.
    Badalov ST, Basitova SM, Godunova LI (1962) Distribution of rhenium in central Asia molybdenite. Geokhimiya 9:813–817Google Scholar
  14. 14.
    Riley GH (1967) Rhenium concentration in Australian molybdenites by stable isotope dilution. Geochim Cosmochim Acta 31:1489–1497CrossRefGoogle Scholar
  15. 15.
    Fleischer M., 1960: The geochemistry of rhenium—addendum. Econ Geol 55: 607-609.CrossRefGoogle Scholar
  16. 16.
    Ishihara S (1988) Rhenium contents of molybdenites in granitoid-series rocks in Japan. Econ Geol 83:1047–1051MathSciNetCrossRefGoogle Scholar
  17. 17.
    Gustafson L, Hunt J (1975) The porphyry copper deposit at El Salvador, Chile. Econ Geol 70:857–912CrossRefGoogle Scholar
  18. 18.
    McCandless TE, Ruiz J, Campbell AR (1993) Rhenium behavior in molybdenite in hypogene and near-surface environments: implications for Re-Os geochronometry. Geochimica et Cosmochimica Acta 57:889–905CrossRefGoogle Scholar
  19. 19.
    Stein H, Schersten A, Hannah J, Markey R (2003) Subgrain-scale decoupling of Re and 187Os and assessment of laser ablation ICP-MS spot dating in molybdenite. Geochim Cosmochim Acta 67:3673–3686CrossRefGoogle Scholar
  20. 20.
    Sinclair W., Jonasson I.R., Kirkham R.V., and Soregaroli A.E., 2009: Rhenium and other platinum-group metals in porphyry deposits. Geol Survey Canada Open File 6181. Google Scholar
  21. 21.
    Sillitoe R, Perello J, Creaser R, Wilton J, Wilson A, Dawborn T (2017) Age of the Zambian Copperbelt. Miner Deposita 52:1245–1268CrossRefGoogle Scholar
  22. 22.
    Kosler J, Simonetti A, Sylvester P, Cox R, Tubrett M, Wilton D (2003) Laser-ablation ICP-MS measurements of Re/Os in molybdenite and implications for Re-Os geochronology. Can Mineral 41:307–320CrossRefGoogle Scholar
  23. 23.
    Lasky S (1950) How tonnage and grade relations help predict ore reserves. Eng Min J 151(4):81–85Google Scholar
  24. 24.
    Singer D (2013) The lognormal distribution of metal resources in mineral deposits. Ore Geol Rev 55:80–86CrossRefGoogle Scholar
  25. 25.
    Babo J, Spandler C, Oliver N, Brown M, Rubenach M, Creaser R (2017) The high-grade Mo-Re Merlin deposit, Cloncurry district, Australia: paragenesis and geochronology of hydrothermal alteration and ore formation. Econ Geol 112:397–422CrossRefGoogle Scholar
  26. 26.
    Stein H, Maarkey R, Morgan J, Du A, Sun Y (1997) Highly precise and accurate Re-Os ages for molybdenite from the East Qinling Molybdenum Belt, Shaanxi Province, China. Econ Geol 92:827–835CrossRefGoogle Scholar
  27. 27.
    Stein H, Markey RJ, Morgan JW, Hannah JL, Scherstén A (2001) The remarkable Re-Os chronometer in molybdenite: how and why it works. Terra Nova 13(6):479–486CrossRefGoogle Scholar
  28. 28.
    Selby D, Creaser R (2001) Re-Os geochronology and systematics in molybdenite from the Endako porphyry molybdenum deposit, British Columbia, Canada. Econ Geol 96:197–204CrossRefGoogle Scholar
  29. 29.
    Golden J, McMillan M, Downs R, Hystad G, Goldstein I, Stein H, Zimmerman A, Sverjensky D, Armstrong J, Hazen R (2013) Rhenium variations in molybdenite (MoS2): Evidence for progressive subsurface oxidation. Earth Planet Sci Lett 366:1–5CrossRefGoogle Scholar
  30. 30.
    Selby D, Creaser R (2004) Macroscale NTIMS and microscale LA-MC-ICP-MS Re-Os isotopic analysis of molybdenite: testing spatial restrictions for reliable Re-Os age determinations, and implications for the decoupling of Re and Os within molybdenite. Geochim Cosmochim Acta 68:3897–3908CrossRefGoogle Scholar
  31. 31.
    Barra F, Ruiz J, Mathur R, Titley S (2003) A Re-Os study of sulfide minerals from the Bagdad porphyry Cu-Mo deposit, northern Arizona, USA. Miner Deposita 38:585–596CrossRefGoogle Scholar
  32. 32.
    Rathkopf C.A., 2015: Distribution of rhenium concentrations in molybdenite among hydrothermal ore deposits. Unpublished M.S. thesis, University of Arizona, 27p and digital appendices.Google Scholar
  33. 33.
    Barton M.D., 2014: Iron oxide(-Cu-Au-REE-P-Ag-U-Co) Systems. Treatise on Geochemistry, 2nd ed., 515-541.CrossRefGoogle Scholar
  34. 34.
    Stein H (2006) Low-rhenium molybdenite by metamorphism in northern Sweden: Recognition, genesis, and global implications. Lithos 87:300–327CrossRefGoogle Scholar
  35. 35.
    Mackenzie J, Canil D (2011) Fluid/melt partitioning of Re, Mo, W, Tl, and Pb in the system haplobasalt-H2O-Cl and the volcanic degassing of trace metals. J Volcanol Geoth Res 204:57–65CrossRefGoogle Scholar
  36. 36.
    Einaudi M, Meinert L, Newberry R (1981) Skarn deposits. In: Skinner B (ed) Economic Geology 75th Anniversary Volume, pp 317–391Google Scholar
  37. 37.
    Burnham C, Ohmoto H (1980) Late-stage processes of felsic magmatism. Min Geol Special Issue 8:1–11Google Scholar
  38. 38.
    Einaudi M, Hedenquist J, Inan E (2003) Sulfidation state of fluids in active and extinct hydrothermal systems: transitions from porphyry to epithermal environments. Soc Econ Geol Geochem Soc Special Pub 10:285–314Google Scholar
  39. 39.
    Seedorff E, Dilles J, Proffett J, Einaudi M, Zurcher L, Stavast W, Johnson D, Barton MD (2005) Porphyry deposits: characteristics and origin of hypogene features. In: Economic Geology 100th Anniversary Volume, vol 29, pp 251–298Google Scholar
  40. 40.
    Sun W, Bennett V, Kamenetsky V (2004) The mechanism of Re enrichment in arc magmas: evidence from Lau Basin basaltic glasses and primitive melt inclusions. Earth Planet Sci Lett 222:101–114CrossRefGoogle Scholar
  41. 41.
    Mao J, Zhang Z, Zhang Z, Du A (1999) Re-Os isotopic dating of molybdenites in the Xioaliugou W (Mo) deposit in the northern Qilian Mountains and its geological significance. Geochim Cosmochim Acta 63:1815–1818CrossRefGoogle Scholar
  42. 42.
    Mao Z, Cheng Y, Liu J, Yuan S, Wu S, Xiang X, Luo X (2013) Geology and molybdenite Re-Os age of the Dahutang granite-related veinlets-disseminated tungsten ore field in the Jiangxin Province, China. Ore Geol Rev 53:422–413CrossRefGoogle Scholar
  43. 43.
    Pasava J, Svojtka M, Veselovsky F, Durisova J, Ackerman L, Pour O, Drabek M, Halodova P, Haluzova E (2016) Laser ablation ICPMS study of trace element chemistry in molybdenite coupled with scanning electron microscopy (SEM)—an important tool for identification of different types of mineralization. Ore Geol Rev 72:874–895CrossRefGoogle Scholar
  44. 44.
    Zhong J, Chen Y, Pirajno F (2017) Geology, geochemistry, and tectonic settings of the molybdenum deposits in South China: a review. Ore Geol Rev 81:829–855CrossRefGoogle Scholar
  45. 45.
    McFall K, Roberts S, McDonald I, Boyce A, Naden J, Teagle D (2019) Rhenium enrichment in the Muratdere Cu-Mo (Au-Re) porphyry deposit, Turkey: evidence from stable isotope analyses (δ34S, δ18O, δD) and laser ablation inductively coupled plasma mass spectrometry analysis of sulfides. Econ Geol.  https://doi.org/10.5382/econgeo.4638 CrossRefGoogle Scholar
  46. 46.
    Xiong Y, Wood S (2002) Experimental determination of the hydrothermal solubility of ReS2 and the Re-ReO2 buffer assemblage and transport of rhenium under supercritical conditions. Geochem Trans 3:1–10CrossRefGoogle Scholar
  47. 47.
    White W, Bookstrom A, Kamilli R, Ganster M, Smith R, Ranta D, Steininger R (1981) Character and origin of climax-type molybdenum deposits. In: Skinner B (ed) Economic Geology 75th Anniversary Volume, pp 270–316Google Scholar
  48. 48.
    Bodnar R, Lecumberri-Sanchez P, Moncada D, Steele-MacInnis M (2014) Fluid inclusions in hydrothermal ore deposits. In: Treatise on Geochemistry, 2nd edn, pp 119–142CrossRefGoogle Scholar
  49. 49.
    Candela PA, Holland HD (1986) A mass transfer model for copper and molybdenum in magmatic hydrothermal systems: the origin of porphyry-type ore deposits. Econ Geol 81:1–19CrossRefGoogle Scholar
  50. 50.
    Fournier R (1999) Hydrothermal processes related to movement of fluid from plastic into brittle rock in the magmatic-epithermal environment. Econ Geol 94:1193–1211CrossRefGoogle Scholar
  51. 51.
    Bernard A, Symonds RB, Rose WI (1990) Volatile transport and deposition of Mo, W and Re in high temperature magmatic fluids. Appl Geochem 5:317–326CrossRefGoogle Scholar
  52. 52.
    Korzhinsky MA, Tkachenko SI, Shmulovich KI, Taran Y, Steinberg GS (1994) Discovery of a pure rhenium mineral at Kudriavy Volcano. Nature 369:51–52CrossRefGoogle Scholar
  53. 53.
    Burt D (1981) Acidity-salinity diagrams—application to greisen and porphyry deposits. Econ Geol 76:832–843CrossRefGoogle Scholar
  54. 54.
    Kovalenker V, Laputina I, Vyal’sov L (1974) Rhenium-rich molybdenite from the Talnakh copper-nickel deposit (Noril’sk region). Doklady Akademii Nauk SSSR 217:187–189Google Scholar
  55. 55.
    Arndt N, Czamanske G, Walker R, Chauvel C, Fedorenko V (2003) Geochemistry and origin of the intrusive hosts of the Noril’sk-Talnakh Cu-Ni-PGE sulfide deposits. Econ Geol 98:495–515Google Scholar
  56. 56.
    Li Y (2014) Comparative geochemistry of rhenium in oxidized arc magmas and MORB and rhenium partitioning during magmatic differentiation. Chem Geol 386:101–114CrossRefGoogle Scholar
  57. 57.
    Colodner D, Sachs J, Ravizza G, Turekian K, Edmond J, Boyle E (1993) The geochemical cycle of rhenium: a reconnaissance. Earth Planet Sci Lett 117:205–221CrossRefGoogle Scholar
  58. 58.
    Xiong Y, Wood S (2001) Hydrothermal transport and deposition of rhenium under subcritical conditions (up to 200 °C) in light of experimental studies. Econ Geol 96:1429–1444Google Scholar
  59. 59.
    Helz GR, Dolor MK (2012) What regulates rhenium deposition in euxinic basins? Chem Geol 304-305:131–141CrossRefGoogle Scholar
  60. 60.
    Taran Y, Hedenquist J, Korzhinsky M, Tkachenko S, Shmulovich K (1995) Geochemistry of magmatic gases from Kudryavy Volcano, Iturup, Kuril Islands. Geochim Cosmochim Acta 59:1749–1761CrossRefGoogle Scholar
  61. 61.
    Crowe B, Finnegan D, Zoller W, Boynton W (1987) Trace element geochemistry of volcanic gases and particles from 1983-1984 eruptive episodes of Kilauea Volcano. J Geophys Res 92:13708–13714CrossRefGoogle Scholar
  62. 62.
    Zelenski M, Malik N, Taran Y (2014) Emissions of trace elements during the 2012-2013 effusive eruption of Tolbachik Volcano, Kamchatka: enrichment factors, partition coefficients and aerosol contribution. J Volcanol Geoth Res 285:136–149CrossRefGoogle Scholar
  63. 63.
    Germani M, Small M, Zoller W, Moyers J (1981) Fractionation of elements during copper smelting. J Am Chem Soc 15(3):299–305Google Scholar

Copyright information

© Society for Mining, Metallurgy & Exploration Inc. 2019

Authors and Affiliations

  1. 1.Lowell Institute for Mineral ResourcesUniversity of ArizonaTucsonUSA
  2. 2.Department of Mining and Geological EngineeringUniversity of ArizonaTucsonUSA
  3. 3.Department of GeosciencesUniversity of ArizonaTucsonUSA
  4. 4.Hecla MiningWinnemuccaUSA

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