Skip to main content
Log in

The Zr/Hf ratio as a fractionation indicator of rare-metal granites

  • Published:
Petrology Aims and scope Submit manuscript

Abstract

The Zr-Hf geochemical indicator, i.e., the Zr/Hf ratio (in wt %) in granitic rocks is proposed to be used as the most reliable indicator of the fractionation and ore potential of rare-metal granites. It was empirically determined that the fractional crystallization of granitic magma according to the scheme granodiorite → biotite granite → leucogranite → Li-F granite is associated with a decrease in the Zr/Hf ratio of the granites. The reason for this is the stronger affinity of Hf than Zr to granitic melt. This was confirmed by experiments on Zr and Hf distribution between granitic melt and crystals of Hf-bearing zircon (T = 800°C, P= 1 kbar). The application of the Zr/Hf indicator was tested at three classic territories of rare-metal granites: eastern Transbaikalia, central Kazakhstan, and the Erzgebirge in the Czech Republic and Germany. The reference Kukul’bei complex of rare-metal granites in eastern Transbaikalia (J3) is characterized by a uniquely high degree of fractionation of the parental granitic melt, with the granites and their vein derivatives forming three intrusive phases. The biotite granites of phase 1 are barren, the leucogranites of phase 2 are accompanied by greisen Sn-W mineral deposits (Spokoininskoe and others), and the final dome-shaped stocks of amazonite Li-F granites of phase 3 host (in their upper parts) Ta deposits of the “apogranite” type: Orlovka, Etyka, and Achikan. The Kukul’bei Complex includes also dikes of ongonites, elvanes, amazonite granites, and miarolitic pegmatites. All granitic rocks of the complex are roughly coeval and have an age of 142±0.6 Ma. The Zr/Hf ratio of the rocks systematically decreases from intrusive phase 1 (40–25) to phases 2 (20–30) and 3 (10–2). Compared to other granite series, the granites of the Kukul’bei Complex are enriched in Rb, Li, Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but are depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. From earlier to later intrusive phases, the rocks become progressively more strongly enriched or depleted in these elements, and their Zr/Hf ratio systematically decreases from 40 to 2. This ratio serves as a reliable indicator of genetic links, degree of fractionation, and rare-metal potential of granites. Greisen Sn, W, Mo, and Be deposits are expected to accompany granites with Zr/Hf < 25, whereas granites related to Ta deposits should have Zr/Hf < 5.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. A. M. Aksyuk, “Experimentally Established Geofluorimeters and the Fluorine Regime in Granite-Related Fluids,” Petrologiya 10(6), 630–644 (2002) [Petrology 10, 557–569 (2002)].

    Google Scholar 

  2. I. V. Aleksandrov, On Geochemistry of Trace and ore Elements in Granitoids (Nauka, Moscow, 1980) [in Russian].

    Google Scholar 

  3. V. F. Barabanov, Mineralogy of Tungsten Deposits of Eastern Transbaikalia. Bukuka, Belukha (Leningradskii Univ., Leningrad, 1961) [in Russian].

    Google Scholar 

  4. E. V. Barbashev and N. A. Trushchova, 1: 200000 State Geological Map of the USSR. Eastern Transbaikalia Series. Sheet M-50-VII (Aginskoe) (Aerogeologiya, Moscow, 1974) [in Russian].

    Google Scholar 

  5. S. M. Beskin, A. M. Grebennikov, and V. V. Matias, “The Khangilai Granite Pluton and Related Orlovka Tantalium Deposit, Transbaikalia,” Petrologiya 2(1), 68–87 (1994a).

    Google Scholar 

  6. S. M. Beskin, V. E. Zagorskii, L. G. Kuznetsova, et al., “Etyka Rare-Metal Ore Field in Eastern Transbaikalia, Eastern Siberia,” Geol. Rudn. Mestorozhd. 36(4), 310–325 (1994b).

    Google Scholar 

  7. S. M. Beskin, V. N. Larin, and Yu. B. Marin, Rare-Metal Granite Formations (Nedra, Leningrad, 1979) [in Russian].

    Google Scholar 

  8. A. A. Beus and A. A. Sitnin, “Geochemical Features of the Granitoids of the Kukul’bei Intrusive Complex in Eastern Transbaikalia,” Sov. Geol., No. 9, 105–107 (1967).

  9. L. S. Borodin and L. N. Ginzburg, “Geochemistry of Peraluminous Rare-Metal Leucogranites: Evolutionary Petrochemical Trend and Correlation between Trace Elements,” Geokhimiya, No. 9, 933–945 (2002) [Geochem. Int. 40, 843–854 (2002)].

  10. V. Yu. Chevychelov, G. P. Zaraisky, S. E. Borisovskii, and D. A. Borkov, “Effect of Melt Composition and Temperature on the Partitioning of Ta, Nb, Mn, and F between Granitic (Alkaline) Melt and Fluorine-Bearing Aqueous Fluid: Fractionation of Ta and Nb and Conditions of Ore Formation in Rare-Metal Granites,” Petrologiya 13(4), 339–357 (2005) [Petrology 13, 305–321–569 (2005)].

    Google Scholar 

  11. V. F. Efimov, Yu. I. Filippova, N. A. Akelin, et al., Criteria for the Prediction of, Exploration for, and Prospective Evaluation of Deposits of Rare-Metal Alkali-Earth Granites: Methodological Recommendations (IMGRE, Moscow, 1992) [in Russian].

    Google Scholar 

  12. B. A. Gaivoronskii, “Bukukin Deposit,” in Mineral Deposits in Transbaikalia (Geoinformmark, Chita-Moskva, 1995), Vol. 1, Book 1, pp. 146–148 [in Russian].

    Google Scholar 

  13. T. I. Getmanskaya and B. S. Chernov, Tin-Tungsten Formation. Conditions of the Formation and Exploration Criteria of the Economic Tungsten Deposits of Transbaikalia (VIMS, Moscow, 1976) [in Russian].

    Google Scholar 

  14. A. M. Grebennikov, “Orlovka Tantalum Deposit,” in Deposits of Transbaikalia (Geoinformmark, Chita-Moskva, 1995b), Vol. 1, Book 2, pp. 96–107 [in Russian].

    Google Scholar 

  15. A. M. Grebennikov, “Spokoininskoe Tungsten Deposit,” in Mineral Deposits in Transbaikalia (Geoinformmark, Chita-Moskva, 1995a), Vol. 1, Book 1, pp. 106–116 [in Russian].

    Google Scholar 

  16. V. N. Koreneva (Devyatova) and G. P. Zaraisky, “Experimental Study of the Solubility of High-Hafnium Zircons in the Fluorine-Bearing Granitoid Melts,” in Geochemistry of Magmatic Rocks (Izd-vo Kol’skogo NTs RAN, Apatity, 2003), pp. 80–82 [in Russian].

    Google Scholar 

  17. Yu. A. Kostitsyn, G. P. Zaraiskii, A. M. Aksyuk, and V. Yu. Chevychelov, “Rb-Sr Evidence for Genetic Links between Biotite and Li-F Granites: An Example of the Spokoinoe, Orlovka, and Etyka Deposits, Eastern Transbaikalia,” Geokhimiya, No. 9, 940–948 (2004) [Geochem. Int. 42, 822–830 (2004)].

  18. P. V. Koval’, Petrology and Geochemistry of Alibitized Granites (Nauka, Novosibirsk, 1975) [in Russian].

    Google Scholar 

  19. P. V. Koval’, Regional Geochemical Analysis of Granitoids (Izd-vo SO RAN NITs OIGGM, Novosibirsk, 1998) [in Russian].

    Google Scholar 

  20. V. I. Kovalenko, Petrology and Geochemistry of Rare-Metal Granitoids (Nauka, Novosibirsk, 1977) [in Russian].

    Google Scholar 

  21. V. I. Kovalenko, Yu. A. Kostitsyn, V. V. Yarmolyuk, et al., “Magma Sources and the Isotopic (Sr and Nd) Evolution of Li-F Rare-Metal Granites,” Petrologiya 7(4), 401–429 (1999) [Petrology 7, 383–409 (1999)].

    Google Scholar 

  22. V. D. Kozlov and L. N. Svadkovskaya, Petrochemistry, Geochemistry, and Ore Potential of Granitoids in Central Transbaikalia (Nauka, Novosibirsk, 1977) [in Russian].

    Google Scholar 

  23. O. D. Levitskii, V. V. Aristov, R. M. Konstantinov, and E. A. Stankeev, Etyka Tin-Bearing Deposits in Eastern Transbaikalia (Akad. Nauk SSSR, Moscow, 1963) [in Russian].

    Google Scholar 

  24. R. L. Linnen, “The Solubility of Nb-Ta-Zr-Hf-W in Granitic Melt with Li and Li + F: Constraints for Miner alization in Rare Metal Granite and Pegmatite,” Econ. Geol. 93, 1013–1025 (1998).

    Google Scholar 

  25. E. N. Lishnevskii and S. M. Beskin, Volume Structure and Spatial Position of Tin-Bearing and Rare-Metal Districts. Deep-Seated Conditions of Ore Formation (Nauka, Moscow, 1986) [in Russian].

    Google Scholar 

  26. D. A. C. Manning, “The Effect of Fluorine on Liquidus Phase Relationship in the System Qz-Ab-Or with Excess Water at 1 kb,” Contrib. Mineral. Petrol. 76, 206–215 (1981).

    Article  Google Scholar 

  27. E. V. Negrei, A. Z. Zhuravlev, V. I. Kovalenko, et al., “Isotopic (Rb-Sr, σ18O) Studies of the Dome of Tantalum-Bearing Lithium-Fluorine Granites, Dokl. Akad. Nauk 342(4), 322–325 (1995).

    Google Scholar 

  28. L. Raimbault, M. Cuney, C. Azencott, et al., “Geochemical Evidence for a Multistage Magmatic Genesis of Ta-Sn-Li Mineralization in the Granite at Beauvoir, French Massif Central,” Econ. Geol. 90, 548–576 (1995).

    Article  Google Scholar 

  29. F. G. Reyf, R. Seltmann, G. P. Zaraisky, “The Role of Magmatic Processes in Formation of Banded Li, FEnriched Granites from the Orlovka Tantalum Deposit, Transbaikalia, Russia: Microthermometric Evidence,” Can. Mineral. 38, 915–936 (2000).

    Article  Google Scholar 

  30. I. G. Rutshtein, G. I. Bogach, and E. L. Vinnichenko, 1: 200000 State Geological Map of the Russian Federation. Argun Area Series. Sheet M-50-IX (Kalangui) (St. Petersburg, VSEGEI, 2001) [in Russian].

    Google Scholar 

  31. L. F. Syritso, Meosozoic Granitoids of the Eastern Transbaikalia and Problems of Rare-Metal Ore Formation (Izd-vo SPbU, St. Petersburg, 2002) [in Russian].

    Google Scholar 

  32. L. V. Tauson, G. M. Gundobin, and L. D. Zorina, Geochemical Fields of Ore-Magmatic Systems (Nauka, Novosibirsk, 1987) [in Russian].

    Google Scholar 

  33. S. R. Taylor and S. M. McLennan, The Continental Crust: Its Composition and Evolution (Blackwell, Oxford, 1985; Mir, Moscow, 1988).

    Google Scholar 

  34. Yu. P. Troshin, V. I. Grebenshchikova, and S. M. Boiko, Geochemistry and Petrology of Rare-Metal Plumasite Granites (Nauka, Novosibirsk, 1983) [in Russian].

    Google Scholar 

  35. N. A. Trushcheva and K. K. Anashkina, 1: 200000 State Geological Map of the USSR. Eastern Transbaikalia Series. Sheets M-50-XY and XXI (Borzya and Dauriya) (Aerogeologiaya, Moscow, 1981) [in Russian].

    Google Scholar 

  36. G. P. Zaraisky and A. M. Aksyuk, “Petrogenesis of Rare-Metal Calc-Alkaline Granites,” in Proceedings of 10th All-Russia Petrographic Conference of Petrography on the Turn of 21st Century. Petrology and Ore Potential of the CIS Regions and Baltic Shield. Apatity, Russia, 2005 (Apatity, 2005) [in Russian].

  37. G. P. Zaraisky, “Problems of the Formation of Tantalum Deposits in the Domes of Li-F Granites with Allowance for Experimental Data,” in Applied Geochemistry. Vol. 7, Book 2. Genetic Types of Deposits (IMGRE, Moscow, 2005), pp. 144–161 [in Russian].

    Google Scholar 

  38. G. P. Zaraisky, “Conditions of the Formation of Rare-Metal Deposits Related to Granitoid Magmatism,” in Smirnov’s Articles-2004 (V.I. Smironov Academician Foundation, Moscow, 2004), pp. 105–192 [in Russian].

    Google Scholar 

  39. G. P. Zaraisky, A. M. Aksyuk, R. Zel’tmann, and A. V. Fed’kin, “Evolution of Rare-Metal Granites and the Zr/Hf Ratio as Indicator of Degree of Crystallization Differentiation,” in Proceedings of 2nd All-Russian Petrographic Conference on Petrography in the Turn of 21st Century. Summary and Prospects, Syktyvkar, Russia, 2000 (Syktyvkar, 2000), Vol. 3, pp. 47–50 [in Russian].

    Google Scholar 

  40. G. P. Zaraisky, A. M. Aksyuk, V. Yu. Chevychelov, et al., “Physicochemical Genetic Model of the Tantalum Deposits Related to the Lithium-Fluorine Granites,“ in Proceedings of Scientific Conference Dedicated to the 100th Anniversary of Academician F. I. Chukhrov. Problems of the Geology of Ore Deposits, Mineralogy, Petrography, and Geochemistry, Moscow, Russia, 2008 (IGEM RAN, Moscow, 2008), pp. 74–77 [in Russian].

    Google Scholar 

  41. G. P. Zaraisky, A. M. Aksyuk, Yu. B. Shapovalov, et al., “Petrography and Geochemistry of Li-F Granites and Pegmatite-Aplite Banded Rocks from the Orlovka and Etyka Tantalum Deposits in Eastern Transbaikalia, Russia,” in Proceedings of the Fourth SGA Meeting. Mineral Deposits: Research and Exploration. Where do They Meet?, Rotterdam, Netherlands, 1997 (Balkema, Rotterdam, 1997), pp. 695–698.

    Google Scholar 

  42. G. P. Zaraisky, V. S. Korzhinskaya, and N. P. Kotova, “The Problem of Hydrothermal Transport of Tantalum and Niobium in ‘Apogranites’ on Experimental Data,” in 12th Quadrennial IAGOD Symposium on Understanding the Genesis of Ore Deposits to Meet the Demands of the 21st Century, Moscow, Russia, 2006 (Moscow, 2006), CD-043.

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to G. P. Zaraisky.

Additional information

Original Russian Text © G.P. Zaraisky, A.M. Aksyuk, V.N. Devyatova, O.V. Udoratina, V.Yu. Chevychelov, 2009, published in Petrologiya, 2009, Vol. 17, No. 1, pp. 28–50.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zaraisky, G.P., Aksyuk, A.M., Devyatova, V.N. et al. The Zr/Hf ratio as a fractionation indicator of rare-metal granites. Petrology 17, 25–45 (2009). https://doi.org/10.1134/S0869591109010020

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S0869591109010020

Keywords

Navigation