Mineralogy and Petrology

, Volume 110, Issue 4, pp 547–560 | Cite as

Trace element composition of rutile and Zr-in-rutile thermometry in meta-ophiolitic rocks from the Kazdağ Massif, NW Turkey

  • Fırat ŞengünEmail author
  • Thomas Zack
Original Paper


In northwest Turkey, ophiolitic meta-gabbros are exposed on the Kazdağ Massif located in the southern part of the Biga Peninsula. Trace element composition of rutile and Zr-in-rutile temperatures were determined for meta-gabbros from the Kazdağ Massif. The Zr content of all rutiles range from 176 to 428 ppm and rutile grains usually have a homogeneous Zr distribution. The rutile grains from studied samples in the Kazdağ Massif are dominated by subchondritic Nb/Ta (11–19) and Zr/Hf ratios (20–33). Nb/Ta and Zr/Hf show positive correlation, which is probably produced by silicate fractionation. The Nb/Ta and Zr/Hf ratios increase with a decrease in Ta and Hf contents. The core of rutile grains are generally characterized by low Nb/Ta ratios of 17–18 whereas the rims exhibit relatively high Nb/Ta ratios of 19–23. Trace element analyses in rutile suggest that these rutile grains were grown from metamorphic fluids. The P-T conditions of meta-gabbros were estimated by both Fe–Mg exchange and Zr-in-rutile thermometers, as well as by the Grt-Hb-Plg-Q geothermobarometer. The temperature range of 639 to 662 °C calculated at 9 kbar using the Zr-in-rutile thermometer is comparable with temperature estimates of the Fe-Mg exchange thermometer, which records amphibolite-facies metamorphism of intermediate P-T conditions. The P-T conditions of meta-ophiolitic rocks suggest that they occur as a different separate higher-pressure tectonic slice in the Kazdağ metamorphic sequence. Amphibolite-facies metamorphism resulted from northward subduction of the İzmir-Ankara branch of the Neo-Tethyan Ocean under the Sakarya Zone. Metamorphism was followed by internal imbrication of the Kazdağ metamorphic sequence resulting from southerly directed compression during the collision.


Rutile Metamorphic Fluid Tectonic Slice Sakarya Zone Biga Peninsula 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



This study was supported by National Postdoctoral Research Scholarship Programme and the Scientific and Technological Research Council of Turkey (TÜBİTAK) grant 114Y834. We thank David Cornell for helping with SEM analyses. We would like to thank two anonymous reviewers and Johann Raith for valuable suggestions and editorial handling of manuscript.


  1. Austrheim H, Putnis CV, Engvik AK, Putnis A (2008) Zircon coronas around Fe-Ti oxides: a physical reference frame for metamorphic and metasomatic reactions. Contrib Mineral Petrol 156:517–527CrossRefGoogle Scholar
  2. Aysal N, Ustaömer T, Öngen S, Keskin M, Köksal S, Peytcheva I, Fanning M (2012) Origin of the Early-Middle Devonian Magmatism in the Sakarya Zone, Nw Turkey: Geochronology, Geochemistry and Isotope Systematics. J Asian Earth Sci 45:201–222CrossRefGoogle Scholar
  3. Baldwin JA, Brown M (2008) Age and duration of ultrahigh-temperature metamorphism in the Anápolis Itauçu complex, Southern Brasília Belt, Central Brazil – constraints from U-Pb geochronology, mineral rare earth element chemistry and trace element thermometry. J Metamorph Geol 26:213–233CrossRefGoogle Scholar
  4. Beccaletto L, Jenny C (2004) Geology and correlation of the ezine zone: A Rhodope Fragment in NW Turkey? Turk J Earth Sci 13:145–176Google Scholar
  5. Bingöl E (1969) Kazdağ Masifi’nin Merkezi ve GD Kesiminin Jeolojisi. MTA Dergisi 72:110–123Google Scholar
  6. Blundy JD, Holland TJB (1990) Calcic amphibole equilibria and a new amphibole-plagioclase geothermometer. Contrib Mineral Petrol 104:208–224CrossRefGoogle Scholar
  7. Brenan JM, Shaw HF, Phinney DL, Ryerson FJ (1994) Rutile-aqueous fluid partitioning of Nb, Ta, Hf, Zr, U and Th: implications for high field strength element depletions in island-arc basalts. Earth Planet Sci Lett 128:327–339CrossRefGoogle Scholar
  8. Cavazza W, Okay AI, Zattin M (2009) Rapid early-middle exhumation of the Kazdağ Massif (Western Anatolia). Int J Earth Sci 98:1935–1947CrossRefGoogle Scholar
  9. Deer WA, Howie RA, Zussman J (1992) An introduction to Rock-forming minerals. Longman Group, Harlow, UKGoogle Scholar
  10. Ding X, Lundstrom C, Huang F, Li J, Zhang ZM, Sun XM, Liang JL, Sun WD (2009) Natural and experimental constraints on formation of the continental crust based on niobium-tantalum fractionation. Int Geol Rev 51:473–501CrossRefGoogle Scholar
  11. Ding X, Hu YH, Zhang H, Li CY, Ling MX, Sun WD (2013) Major Nb/Ta fractionation recorded in garnet amphibolite facies metagabbro. J Geol 121:255–274CrossRefGoogle Scholar
  12. Dürr S, Alther R, Keller J, Okrusch M, Seidel E (1978) The median Aegean crystalline belt: Stratigraphy, structure, metamorphism, magmatism. In: Closs H, Roeder D, Schmidt K (eds) Alps, appenines and hellenides. Schweizerbart, Stuttgart, pp. 455–476Google Scholar
  13. Duru M, Pehlivan Ş, Şentürk Y, Yavaş F, Kar H (2004) New results on the lithostratigraphy of the Kazdağ Massif in Northwest Turkey. Turk J Earth Sci 13:177–186Google Scholar
  14. Eggins S, Kinsley L, Shelley J (1998) Deposition and element fractionation processes during atmospheric pressure laser sampling for analysis by ICP-MS. Appl Surf Sci 127:278–286CrossRefGoogle Scholar
  15. Ellis DJ, Green DH (1979) An experimental study of the effect of Ca upon garnet-clinopyroxene Fe–Mg exchange equilibria. Contrib Mineral Petrol 71:12–22CrossRefGoogle Scholar
  16. Erdoğan B, Akay E, Hasözbek A, Satır M, Siebel W (2013) Stratigraphy and tectonic evolution of the Kazdağ Masif (NW Anatolia) based on field studies and radiometric ages. Int Geol Rev 55:2060–2082CrossRefGoogle Scholar
  17. Ewing TA, Herman J, Rubatto D (2013) The robustness of the Zr-in-rutile and Ti-in-zircon thermometers during high-temperature metamorphism (Ivrea-Verbano zone, Northern Italy). Contrib Mineral Petrol 165:757–779CrossRefGoogle Scholar
  18. Ferry JM, Spear FS (1978) Experimental calibration of the partitioning of Fe and Mg between biotite and garnet. Contrib Mineral Petrol 66:113–117CrossRefGoogle Scholar
  19. Ferry JM, Watson EB (2007) New thermodynamic models and revised calibrations for the Ti-in-zircon and Zr-in-rutile thermometers. Contrib Mineral Petrol 154:429–437CrossRefGoogle Scholar
  20. Foley SF, Barth MG, Jenner GA (2000) Rutile/melt partition coefficients for trace elements and assessment of the influence of rutile on the trace element characteristics of subduction zone magmas. Geochim Cosmochim Act 64:933–938CrossRefGoogle Scholar
  21. Foley S, Tiepolo M, Vannucci R (2002) Growth of early continental crust controlled by melting of amphibolite in subduction zones. Nature 417:837–840CrossRefGoogle Scholar
  22. Frey FA, Green DH, Roy SD (1978) Integrated Models of Basalt Petrogenesis - Study of Quartz Tholeiites to Olivine Melilities from South Eastern Australia Utilizing Geochemical and Experimental Petrological Data. J Petrol 19:463--513Google Scholar
  23. Gao XY, Zheng FY, Xia XP, Chen YP (2014) U-Pb ages and trace element of metamorphic rutile from ultrahigh-pressure quartzite in the Sulu orogen. Geochim Cosmochim Acta 143:87–114CrossRefGoogle Scholar
  24. Graham J, Morris RC (1973) Tungsten- and antimony substituted rutile. Mineral Mag 39:470–473CrossRefGoogle Scholar
  25. Green TH (1995) Significance of Nb/Ta as an indicator of geochemical processes in the crust–mantle system. Chem Geol 120:347–359CrossRefGoogle Scholar
  26. Hermann J, Spandler C, Hack A, Korsakov A (2006) Aqueous fluids and hydrous melts in high-pressure and ultra-high pressure rocks: implications for element transfer in subduction zones. Lithos 92:399–417CrossRefGoogle Scholar
  27. Hodges KV, Spear FS (1982) Geothermometry, geobarometry and the Al2 SiO5 triple point at Mt. Moosilauke, New Hampshire. Am Mineral 67:118–34Google Scholar
  28. Holland TJB, Powell R (1990) An enlarged and updated internally consistent thermodynamic data set with uncertainties and correlations: the system K2O – Na2O – CaO – MgO – MnO – FeO – Fe2O3 – Al2O3 – TiO2 – SiO2 – C – H2O – O2. J Metamorph Geol 8:89–124CrossRefGoogle Scholar
  29. Horng WS, Hess PC (2000) Partition coefficients of Nb and Ta between rutile and anhydrous haplogranite melts. Contrib Mineral Petrol 138:176–185CrossRefGoogle Scholar
  30. Huang J, Xiao YL, Gao YJ, Hou ZH, Wu W (2012) Nb–Ta fractionation induced by fluid-rock interaction in subduction-zones: constraints from UHP eclogite- and vein-hosted rutile from the Dabie orogen, Central-Eastern China. J Metamorph Geol 30:821–842CrossRefGoogle Scholar
  31. Jochum KP, Nehring F (2006) NIST 610: GeoReM preferred values (11/2006). GeoReM
  32. John T, Scherer EE, Haase K, Schenk V (2004) Trace element fractionation during fluid-induced eclogitization in a subducting slab: trace element and Lu-Hf-Sm-Nd isotope systematics. Earth Planet Sci Lett 227:441–456CrossRefGoogle Scholar
  33. John T, Klemd R, Klemme S, Pfander J, Hoffmann J, Gao J (2011) Nb–Ta fractionation by partial melting at the titanite–rutile transition. Contrib Mineral Petrol 161:35–45CrossRefGoogle Scholar
  34. Klemme S, Prowatke S, Hametner K, Gunther D (2005) Partitioning of trace elements between rutile and silicate melts: implications for subduction zones. Geochim Cosmochim Acta 69:2361–2371CrossRefGoogle Scholar
  35. Kohn MJ, Spear FS (1990) Two new geobarometers for garnet amphiboliteso with applications to Southeastern Vermont. Am Mineral 75:89–96Google Scholar
  36. Luvizotto GL, Zack T (2009) Nb and Zr behavior in rutile during high-grade metamorphism and retrogression: An example from the Ivrea–Verbano Zone. Chem Geol 261:303--317Google Scholar
  37. Luvizotto GL, Zack T, Meyer HP, Ludwig T, Triebold S, Kronz A, Munker C, Stockli DF, Prowatke S, Klemme S, Jacob DE, Eynatten H (2009) Rutile crystals as potential trace element and isotope mineral standards for microanalysis. Chem Geol 261:346–369CrossRefGoogle Scholar
  38. Meinhold G (2010) Rutile and its applications in earth sciences. Earth Sci 102:1–28Google Scholar
  39. Meinhold G, Kostopoulos D, Frei D, Himmerkus F, Reischmann T (2010) U-Pb LA-SF-ICP-MS zircon geochronology of the Serbo-Macedonian Massif, Greece: Palaeotectonic constraints for Gondwana-derived terranes in the Eastern Mediterranean. Int J Earth Sci 99:813–832CrossRefGoogle Scholar
  40. Meyer M, John T, Brandt S, Klemd R (2011) Trace element composition of rutile and the application of Zr-in-rutile thermometry to UHT metamorphism (Epupa complex, NW Namibia). Lithos 126:388–401CrossRefGoogle Scholar
  41. Miller C, Zanetti A, Thoni M (2007) Eclogitisation of gabbroic rocks: redistribution of trace elements and Zr in rutile thermometry in an Eo-Alpine subduction zone (Eastern Alps). Chem Geol 239:96–123CrossRefGoogle Scholar
  42. Moix P, Beccaletto L, Kozur H, Hochard C, Rosselet F, Stampfli GM (2008) A new classification of the Turkish terranes and sutures and its implication for the paleotectonic history of the region. Tectonophysics 451:7–39CrossRefGoogle Scholar
  43. MTA (2012) General and economic geology of the Biga Peninsula. Spec Publ Ser 28:326(in Turkish)Google Scholar
  44. Münker C, Pfänder JA, Weyer S, Büchl A, Kleine T, Mezger K (2003) Evolution of planetary cores and the earth–moon system from Nb/Ta systematic. Science 301:84–87CrossRefGoogle Scholar
  45. Okay AI (1984) Distribution and characteristics of the Northwest Turkish blueschists. In: Robertson AHF, Dixon JE (eds) The geological evolution of the Eastern Mediterranean. Geol Soc Spec Publ 17: 455–466Google Scholar
  46. Okay AI (1986) High-pressure/low-temperature metamorphic rocks of Turkey: Geol Soc Am Mem 164: 333–347Google Scholar
  47. Okay AI, Tüysüz O (1999) Tethyan sutures of Northern Turkey. In: Durand B, Jolivet L, Horváth F, Séranne M (eds) The Mediterranean basins: tertiary extension within the alpine orogen, Geol Soc Spec Publ, vol 156, pp. 475–515Google Scholar
  48. Okay AI, Satır M (2000) Coeval plutonism ve metamorphism in a latest Oligocene metamorphic core complex in Northwest Turkey. Geol Mag 137:495–516CrossRefGoogle Scholar
  49. Okay AI, Göncüoğlu MC (2004) The Karakaya complex: A review of data and concepts. Turk J Earth Sci 13:77–95Google Scholar
  50. Okay AI, Siyako M, Bürkan, KA (1991) Geology and tectonic evolution of the Biga Peninsula. In: Dewey JF (eds) Special issue on tectonics. Bull Tech Uni Ist 44: 191–255Google Scholar
  51. Okay AI, Satir M, Siebel W (2006) Pre-alpide and Mesozoic orogenic events in the Eastern Mediterranean region. Geol Soc Spec Publ 32:389–405Google Scholar
  52. Okay AI, Satır M, Maluski H, Siyako M, Monie P, Metzger R, Akyüz S (1996) Paleo-and Neotethyan events in Northwest Turkey. In: Yin A, Harrison M (eds) Tectonics of Asia. Cambridge University Press, Cambridge, pp. 420–441Google Scholar
  53. Pickett EA, Robertson AHF, Dixon JE (1996) The Karakaya complex, NW Turkey: A palaeo tethyan accretionary complex, geology of the Black Sea region. Geol Soc Spec Publ 153:995–1009CrossRefGoogle Scholar
  54. Rudnick RL, Barth M, Horn I, McDonough WF (2000) Rutile-bearing refractory eclogites: missing link between continents and depleted mantle. Science 287:278–281CrossRefGoogle Scholar
  55. Scambelluri M, Bottazzi P, Trommsdorf V, Vannucci R, Hermann J, Gomez-Pugnaire MT, Lopez-Sanchez-Vizcaino V (2001) Incompatible element-rich fluids released by antigorite breakdown in deeply subducted mantle. Earth Planet Sci Lett 192:457–470CrossRefGoogle Scholar
  56. Schmidt MW, Dardon A, Chazot G, Vannucci R (2004) The dependence of Nb and Ta rutile–melt partitioning on melt composition and Nb/Ta fractionation during subduction processes. Earth Planet Sci Lett 226:415–432CrossRefGoogle Scholar
  57. Schmidt A, Weyer S, Mezger K, Scherer EE, Xiao YL, Hoefs J, Brey GP (2008) Rapid eclogitisation of the Dabie-Sulu UHP terrane: constraints from Lu–Hf garnet geochronology. Earth Planet Sci Lett 273:203–213CrossRefGoogle Scholar
  58. Schmidt A, Weyer S, John T, Brey GP (2009) HFSE systematics of rutile-bearing eclogites: new insights into subduction zone processes and implications for the earth’s HFSE budget. Geochim Cosmochim Acta 73:455–468CrossRefGoogle Scholar
  59. Schuiling RD (1959) Über eine präherzynische Faltungsphase im Kazdağ Kristallin. Bull Min Res Exp 53:89–93Google Scholar
  60. Spear FS, Wark DA, Cheney JT (2006) Zr-in-rutile thermometry in blueschists from Sifnos, Greece. Contrib Mineral Petrol 152:375–385CrossRefGoogle Scholar
  61. Stalder R, Foley SF, Brey GP, Horn I (1998) Mineral-aqueous fluid partitioning of trace elements at 900–1200 C and 3.0–5.7 GPa: new experimental data for garnet, clinopyroxene, and rutile, and implications for mantle metasomatism. Geochim Cosmochim Acta 62:1781–1801CrossRefGoogle Scholar
  62. Stepanov AS, Hermann J (2013) Fractionation of Nb and Ta by biotite and phengite: implications for the “missing Nb paradox”. Geology 41:303–306CrossRefGoogle Scholar
  63. Şengör AMC, Yılmaz Y (1981) Tethyan evolution of Turkey: a plate tectonic approach. Tectonophysics 75:181–241CrossRefGoogle Scholar
  64. Şengün F, Yigitbas E, Tunç İO (2011) Geology and tectonic emplacement of eclogite and blueschist, Biga Peninsula, Northwest Turkey. Turk J Earth Sci 20:273–285Google Scholar
  65. Tatsumi Y, Nakamura N (1986) Composition of aqueous fluid from serpentine in the subducted lithosphere. Geochem J 20:191–196CrossRefGoogle Scholar
  66. Tomkins HS, Powell R, Ellis DJ (2007) The pressure dependence of the zirconium-in-rutile thermometer. J Metamorph Geol 25:703–713CrossRefGoogle Scholar
  67. Watson EB, Wark DA, Thomas JB (2006) Crystallization thermometers for zircon and rutile. Contrib Mineral Petrol 151:413–433CrossRefGoogle Scholar
  68. Weyer S, Muenker C, Mezger K (2003) Nb/Ta, Zr/Hf and REE in the depleted mantle: implications for the differentiation history of the crust–mantle system. Earth Planet Sci Lett 205:309–324CrossRefGoogle Scholar
  69. Xia QX, Zheng YF, Hu ZC (2010) Trace elements in zircon and coexisting minerals from low-T/UHP metagranite in the Dabie orogen: implications for action of supercritical fluid during continental subduction-zone metamorphism. Lithos 114:385–412CrossRefGoogle Scholar
  70. Xiao YL, Sun WD, Hoefs J, Simon K, Zhang ZM, Li SG, Hofmann AW (2006) Making continental crust through slab melting: constraints from niobium–tantalum fractionation in UHP metamorphic rutile. Geochim Cosmochim Acta 70:4770–4782CrossRefGoogle Scholar
  71. Xiong XL, Adam J, Green TH (2005) Rutile stability and rutile/melt HFSE partitioning during partial melting of hydrous basalt: implications for TTG genesis. Chem Geol 218:339–359CrossRefGoogle Scholar
  72. Van Achterbergh E, Ryan CG, Griffin WL (2000) GLITTER (Version 3.0, On-line interactive data reduction for LA-ICPMS). Maquarie Research LtdGoogle Scholar
  73. Yiğitbaş E, Şengün F, Tunç İO (2014) Pre-Neogene tectonic units in the Biga Peninsula and an approach to geodynamic evolution of region. TUBITAK project (110Y281)Google Scholar
  74. Zack T, Luvizotto GL (2006) Application of rutile thermometry to eclogites. Miner Petrol 88:69–85CrossRefGoogle Scholar
  75. Zack T, Kronz A, Foley SF, Rivers T (2002) Trace element abundances in rutiles from eclogites and associated garnet mica schists. Chem Geol 184:97–122CrossRefGoogle Scholar
  76. Zack T, Moraes R, Kronz A (2004) Temperature dependence of Zr in rutile: empirical calibration of a rutile thermometer. Contrib Mineral Petrol 148:471–488CrossRefGoogle Scholar
  77. Zhang JX, Yu S, Meng FC, Li JP (2009) Paired high-pressure granulite and eclogite in collision orogens and their geodynamic implications. Acta Petrol Sin 25:2050–2066(in Chinese with English abstract)Google Scholar
  78. Zheng YF, Xia QX, Chen RX, Gao XY (2011) Partial melting, fluid supercriticality and element mobility in ultrahigh-pressure metamorphic rocks during continental collision. Earth Sci 107:342–374Google Scholar

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© Springer-Verlag Wien 2016

Authors and Affiliations

  1. 1.Terzioğlu Campus, Faculty of Engineering, Department of Geological EngineeringÇanakkale Onsekiz Mart UniversityÇanakkaleTurkey
  2. 2.Department of Earth SciencesUniversity of GothenburgGothenburgSweden

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