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Crystallization thermometers for zircon and rutile

  • E. B. WatsonEmail author
  • D. A. Wark
  • J. B. Thomas
Original Paper

Abstract

Zircon and rutile are common accessory minerals whose essential structural constituents, Zr, Ti, and Si can replace one another to a limited extent. Here we present the combined results of high pressure–temperature experiments and analyses of natural zircons and rutile crystals that reveal systematic changes with temperature in the uptake of Ti in zircon and Zr in rutile. Detailed calibrations of the temperature dependencies are presented as two geothermometers—Ti content of zircon and Zr content of rutile—that may find wide application in crustal petrology. Synthetic zircons were crystallized in the presence of rutile at 1–2 GPa and 1,025–1,450°C from both silicate melts and hydrothermal solutions, and the resulting crystals were analyzed for Ti by electron microprobe (EMP). To augment and extend the experimental results, zircons hosted by five natural rocks of well-constrained but diverse origin (0.7–3 GPa; 580–1,070°C) were analyzed for Ti, in most cases by ion microprobe (IMP). The combined experimental and natural results define a log-linear dependence of equilibrium Ti content (expressed in ppm by weight) upon reciprocal temperature:
$$\log ({\text{Ti}}_{{{\text{zircon}}}}) = (6.01 \pm 0.03) - \frac{{5080 \pm 30}}{{T\;(\hbox{K})}}.$$
In a strategy similar to that used for zircon, rutile crystals were grown in the presence of zircon and quartz (or hydrous silicic melt) at 1–1.4 GPa and 675–1,450°C and analyzed for Zr by EMP. The experimental results were complemented by EMP analyses of rutile grains from six natural rocks of diverse origin spanning 0.35–3 GPa and 470–1,070°C. The concentration of Zr (ppm by weight) in the synthetic and natural rutiles also varies in log-linear fashion with T −1:
$$\log ({\text{Zr}}_{{{\text{rutile}}}}) = (7.36 \pm 0.10) - \frac{{4470 \pm 120}}{{T\;(\hbox{K})}}.$$
The zircon and rutile calibrations are consistent with one another across both the synthetic and natural samples, and are relatively insensitive to changes in pressure, particularly in the case of Ti in zircon. Applied to natural zircons and rutiles of unknown provenance and/or growth conditions, the thermometers have the potential to return temperatures with an estimated uncertainty of ±10 ° or better in the case of zircon and ±20° or better in the case of rutile over most of the temperature range of interest (∼400–1,000°C). Estimates of relative temperature or changes in temperature (e.g., from zoning profiles in a single mineral grain) made with these thermometers are subject to analytical uncertainty only, which can be better than ±5° depending on Ti or Zr concentration (i.e., temperature), and also upon the analytical instrument (e.g., IMP or EMP) and operating conditions.

Keywords

Zircon Rutile Minimum Detection Limit Bishop Tuff Rutile Crystal 
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.

Notes

Acknowledgements

A great many people helped to make this work possible. The following individuals graciously provided the samples reported on in this study: E. Baxter (Stillup Tal), M. Hamilton (Skaergaard), B. McDonough, B. Nash, R. Rudnick, S. Sorensen, F. Spear and L. Storm. The following individuals also generously complied with our requests for zircons and rock samples: J. Hanchar, A. Irving, D. Lindsey, R. Kerrich, D. London, G. Pearson, T. Pettke, M. Picard (Canadian Museum of Nature), and D. Rumble. In the end, zircons and rutiles in most of these latter samples were not analyzed because the rocks did not meet the criteria required for inclusion in thermometer calibrations: namely, independently constrained temperature, known or calculable activities of relevant components, and reasonable evidence for lack of inheritance in analyzable portions of the zircons. The analytical aspects of the project were expedited immeasurably by Graham Layne (IMP protocols for Ti in zircons) and also by Lara Storm and Frank Spear, who allowed us to use their unpublished data on Zr in natural rutiles (ADK and SF, respectively). During the course of the project, we benefited from extensive discussions with Daniele Cherniak, Mark Harrison, Joe Pyle, Frank Spear, Lara Storm and Dustin Trail. Helen Tomkins (née Degeling) generously provided access to her unpublished data and contributed significantly to our thinking about the effect of pressure on the Zr-in-rutile thermometer. The manuscript was improved significantly by the critical reviews of Thomas Zack and an anonymous reviewer. This work was supported by the Earth Sciences Division of the National Science Foundation, through grants EAR 0073752 and EAR 0440228 to EBW.

References

  1. Anderson AT, Davis AM, Lu F (2000) Evolution of the Bishop Tuff rhyolitic magma based on melt and magnetite inclusions and zoned phenocrysts. J Petrol 41:449–473CrossRefGoogle Scholar
  2. Belousova EA, Griffin WL, O’Reilly SY, Fisher NJ (2002) Igneous zircon: trace element composition as an indicator of source rock type. Contrib Mineral Petrol 143:602–622Google Scholar
  3. Bingen B, Austrheim H, Whitehouse M (2001) Ilmenite as a source for zirconium during high-grade metamorphism? Textural evidence from the Caledonides of western Norway and implications for zircon geochronology. J Petrol 42:355–375CrossRefGoogle Scholar
  4. Brey G, Köhler T (1990) Geothermobarometry in four-phase lherzolites II: new thermobarometers, and practical assessment of existing thermobarometers. J Petrol 31:1353–1378Google Scholar
  5. Brooks CK (1969) On the distribution of zirconium and hafnium in the Skaergaard intrusion, East Greenland. Geochim Cosmochim Acta 33:357–370CrossRefGoogle Scholar
  6. Byrd BJ, Nash WP (1993) Eruption of rhyolite at the Honeycomb Hills, Utah—cyclical tapping of a zoned silicic magma reservoir. J Geophys Res 98:14075–14090CrossRefGoogle Scholar
  7. Cherniak DJ, Watson EB (2001) Pb diffusion in zircon. Chem Geol 172:5–24CrossRefGoogle Scholar
  8. Cherniak DJ, Hanchar JM, Watson EB (1997a) Diffusion of tetravalent cations in zircon. Contrib Mineral Petrol 127:383–390CrossRefGoogle Scholar
  9. Cherniak DJ, Hanchar JM, Watson EB (1997b) Rare-earth diffusion in zircon. Chem Geol 134:289–301CrossRefGoogle Scholar
  10. Compston W, Williams IS, Meyer C (1984) U–Pb geochronology of zircons from lunar breccia 73217 using a sensitive high mass-resolution ion microprobe. J Geophys Res Suppl 89:B525–B534CrossRefGoogle Scholar
  11. Congdon RD, Nash WP (1991) Eruptive pegmatite magma: rhyolite of the Honeycomb Hills, Utah. Am Mineral 76:1261–1278Google Scholar
  12. Davis WJ (1997) U–Pb zircon and rutile ages from granulite xenoliths in the Slave province: evidence for mafic magmatism in the lower crust coincident with Proterozoic dike swarms. Geology 25:343–346CrossRefGoogle Scholar
  13. Davis GL, Krogh TE, Erlank AJ (1976) The ages of zircons from kimberlites from South Africa. Carnegie Inst Wash Yrbk 75:821–824Google Scholar
  14. Degeling HS (2003) Zr equilibria in metamorphic rocks. Unpublished PhD Thesis, Australian National University, 231 ppGoogle Scholar
  15. Dodson MH (1973) Closure temperature in cooling geochronological and petrological systems. Contrib Mineral Petrol 40:259–274CrossRefGoogle Scholar
  16. Dunbar NW, Hervig RL (1992) Petrogenesis and volatile stratigraphy of the Bishop tuff—evidence from melt inclusion analysis. J Geophys Res 97:15129–15150CrossRefGoogle Scholar
  17. Ghent ED, Stout MZ (1984) TiO2 activity in metamorphosed pelitic and basic rocks—principles and applications to metamorphism in southeastern Canadian cordillera. Contrib Mineral Petrol 86:248–255CrossRefGoogle Scholar
  18. Harrison TM, Aikman A, Holden P, Walker AM, McFarlane C, Rubatto D, Watson EB (2005) Testing the Ti-in-zircon thermometer. Eos Trans AGU (program and abstracts, fall meeting 2005)Google Scholar
  19. Hayden LA, Watson EB, Wark DA (2006) Rutile saturation in hydrous, siliceous melts and its bearing on Ti thermometry of quartz and zircon (in preparation)Google Scholar
  20. Hayden LA, Watson EB, Wark DA (2005) Rutile saturation and TiO2 diffusion in hydrous siliceous melts. Eos Trans AGU (program and abstracts, fall meeting 2005)Google Scholar
  21. Hildreth W (1979) The Bishop Tuff: evidence for the origin of the compositional zonation in silicic magma chambers. Geol Soc Am Spec Paper 180:43–76Google Scholar
  22. Hoskin PWO, Schaltegger U (2003) The composition of zircon and igneous and metamorphic petrogenesis. In: Hanchar JM, Hoskin PWO (eds) Zircon Rev Mineral Geochem, vol 53. Mineral Soc Am, Washington, pp 27–62Google Scholar
  23. Ireland TR, Wlotzska F (1992) The oldest zircons in the solar system. Earth Planet Sci Lett 109:1–10CrossRefGoogle Scholar
  24. Johannes W (1985) The significance of experimental studies for the formation of migmatites. In: Ashworth JR (ed) Migmatites. Chapman and Hall, New York, Blackie, Glasgow, London, pp 36–86Google Scholar
  25. Kennedy GC, Heard HC, Wasserburg GJ, Newton RC (1962) The upper 3-phase region in the system SiO2-H2O. Am J Sci 260:501–521Google Scholar
  26. Kerrich R, King R (1993) Hydrothermal zircon and baddeleyite in Val-d’Or Archean mesothermal gold deposits—characteristics, compositions, and fluid-inclusion properties, with implications for timing of primary gold mineralization. Can J Earth Sci 30:2334–2351Google Scholar
  27. Lee C-T, Rudnick RL (1999) Compositionally stratified cratonic lithosphere: petrology and geochemistry of peridotite xenoliths from the Labait Volcano, Tanzania. In: Gurney JJ, Richardson SR (eds) Proceedngs of seventh international kimberlite conference, Cape Town, South Africa, pp 503–521Google Scholar
  28. Lindsley DH, Brown GM, Muir ID (1969) Conditions of the ferrowollastonite-ferrohedenbergite inversion in the Skaergaard intrusion, East Greenland. Mineral Soc Am Spec Paper 2:193–201Google Scholar
  29. Maas R, Kinny PD, Williams IS, Froude DO, Compston W (1992) The Earth’s oldest known crust: a geochronological and geochemical study of 3900–4200 Ma old zircons from Mt. Narryer and Jack Hills, Western Australia. Geochim Cosmochim Acta 56:1281–1300CrossRefGoogle Scholar
  30. Manchester JE, Cherniak DJ, Watson EB (2006) Diffusion of Zr and Hf in rutile (in preparation)Google Scholar
  31. Mezger K, Hanson GN, Bohlen SR (1989) High-precision U–Pb ages of metamorphic rutile: applications to the cooling history of high-grade terranes. Earth Planet Sci Lett 96:106–118CrossRefGoogle Scholar
  32. Mezger K, Rawnsley C, Bohlen SR, Hanson G (1991) U-Pb garnet, sphene, monazite and rutile ages: implications for the duration of high-grade metamorphism and cooling histories, Adirondack Mountains, New York. J Geol 99:415–428Google Scholar
  33. Mojzsis SJ, Harrison TM, Pidgeon RT (2001) Oxygen-isotope evidence from ancient zircons for liquid water at the Earth’s surface 4300 Myr ago. Nature 409:178–181CrossRefGoogle Scholar
  34. Peppard BT, Steele IM, Davis AM, Wallace PJ, Anderson AT (2001) Zoned quartz phenocrysts from the rhyolitic Bishop tuff. Am Mineral 86:1034–1052Google Scholar
  35. Rudnick RL, Ireland TR, Gehrels G, Irving AJ, Chesley JT, Hanchar JM (1999) In: Gurney JJ, Richardson SR (eds) Proceedings of seventh international kimberlite conference, Cape Town, South Africa, pp 728–735Google Scholar
  36. Ryerson FJ, Watson EB (1987) Rutile saturation in magmas: implications for Ti-Nb-Ta depletion in island-arc basalts. Earth Planet Sci Lett 86:225–239CrossRefGoogle Scholar
  37. Schliestedt M (1986) Eclogite-blueschist relationships as evidenced by mineral equilibria in the high-pressure metabasic rocks of Sifnos (Cycladic Islands), Greece. J Petrol 27:1437–1459Google Scholar
  38. Selverstone J, Morteani G, Staude J-M (1991) Fluid channelling during ductile shearing: transformation of granodiorite into aluminous schist in the Tauern Window, Eastern Alps. J Metamorph Geol 9:419–431CrossRefGoogle Scholar
  39. Sorensen SS, Barton MD (1987) Metasomatism and partial melting in a subduction complex: Catalina schist, southern California. Geology 15:115–118CrossRefGoogle Scholar
  40. Sorensen SS, Grossman JN (1989) Enrichment of trace elements in garnet amphibolites from a paleo-subduction zone: Catalina Schist, southern California. Geochim Cosmochim Acta 53:3155–3177CrossRefGoogle Scholar
  41. Spear FS, Kohn MJ, Cheney JT, Florence F (2002) Metamorphic, thermal and tectonic evolution of central New England. J Petrol 43:2097–2120CrossRefGoogle Scholar
  42. Spear FS, Wark DA, Cheney JT, Schumacher J, Watson EB (2006) Zr-in-rutile thermometry of blueschists from Sifnos, Greece. Contrib Mineral Petrol (submitted)Google Scholar
  43. Speer JA (1982) Zircon. In: Ribbe PH (ed) Orthosilicates Rev Mineral, vol 5. Mineral Soc Am, Washington, pp 67–112Google Scholar
  44. Storm LC, Spear FS (2005) Pressure, temperature and cooling rates of granulite facies migmatitic pelites from the southern Adirondack Highlands, New York. J Metamorph Geol 23:107–130CrossRefGoogle Scholar
  45. Trail D, Mojzsis SJ, Harrison TM (2004) Inclusion mineralogy of pre-4.0 Ga zircons from Jack Hills, Western Australia: a progress report. Geochim Cosmochim Acta 68(Goldschmidt Conf Abstr):A743Google Scholar
  46. Turner G, Harrison TM, Holland G, Mojzsis SJ, Gilmour J (2004) Extinct 244Pu in ancient zircons. Science 306:89–91CrossRefGoogle Scholar
  47. Wager LR, Brown GM (1968) Layered igneous rocks. Oliver and Boyd, EdinburghGoogle Scholar
  48. Wallace PJ, Anderson AT, Davis AM (1999) Gradients in H2O, CO2 and exsolved gas in a large-volume silicic magma system: interpreting the record preserved in melt inclusions from the Bishop Tuff. J Geophys Res 104:20097–20122CrossRefGoogle Scholar
  49. Wark DA, Watson EB (2004) Launching the TITANiQ: a titanium-in-quartz thermometer. Geochim Cosmochim Acta 68(Goldschmidt Conf Abstr):A543Google Scholar
  50. Wark DA, Anderson AT, Watson EB (2004) Probing Ti in Quartz: application of the TITANiQ thermometer to the Bishop Tuff. EOS Trans Am Geophys Union (joint assembly program and abstracts)Google Scholar
  51. Watson EB, Harrison TM (1983) Zircon saturation revisited: temperature and composition effects in a variety of crustal magma types. Earth Planet Sci Lett 64:295–304CrossRefGoogle Scholar
  52. Watson EB, Harrison TM (2005) Zircon thermometer reveals minimum melting conditions on earliest Earth. Science 308:841–844CrossRefGoogle Scholar
  53. Watson EB, Lupulescu A (1993) Aqueous fluid connectivity and chemical transport in clinopyroxene-rich rocks. Earth Planet Sci Lett 117:279–294CrossRefGoogle Scholar
  54. Watson EB, Cherniak DJ, Hanchar JM, Harrison TM, Wark DA (1997) The incorporation of Pb into zircon. Chem Geol 141:19–31CrossRefGoogle Scholar
  55. Wiedenbeck M, Allé P, Corfu F, Griffin WL, Meier M, Oberli F, von Quadt A, Roddick JC, Spiegel W (1995) Three natural zircon standards for U-Th-Pb, Lu-Hf, trace element and REE analyses. Geostand Newslett 19:1–23CrossRefGoogle Scholar
  56. Wilde SA, Valley JW, Peck WH, Graham CM (2001) Evidence from detrital zircons for the existence of continental crust and oceans on the Earth 4.4 Ga ago. Nature 409:175–178CrossRefGoogle Scholar
  57. Wilson CJN, Hildreth W (1997) The Bishop Tuff: new insights from eruptive stratigraphy. J Geol 105:407–439CrossRefGoogle Scholar
  58. Wong L, Davis DW, Krogh TE, Robert F (1991) U-Pb zircon and rutile geochronology of Archean greenstone formation and gold mineralization in the Val d’Or region, Quebec. Earth Planet Sci Lett 104:325–336CrossRefGoogle Scholar
  59. Wyllie PJ (1983) Experimental and thermal constraints on the deep-seated parentage of some granitoid magmas in subduction zones. In: Atherton MP, Gribble CD (eds) Migmatites, melting and metasomatism. Shiva, Cheshire, pp 37–51Google Scholar
  60. 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
  61. Zack T, Moraes R, Kronz A (2004) Temperature dependence of Zr in rutile: empirical calibration of a rutile thermometer. Contrib Mineral Petrol 148:471–488Google Scholar

Copyright information

© Springer-Verlag 2006

Authors and Affiliations

  1. 1.Department of Earth & Environmental SciencesRensselaer Polytechnic InstituteTroyUSA

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