Contributions to Mineralogy and Petrology

, Volume 113, Issue 2, pp 208–225

Resetting of oxybarometers and oxygen isotope ratios in granulite facies orthogneisses during cooling and shearing, Adirondack Mountains, New York

  • Ian Cartwright
  • John W. Valley
  • Anne-Marie Hazelwood


The petrography, petrology, and oxygenisotope geochemistry of granulite-facies granitic and syenitic orthogneisses of the Diana and Stark complexes, Adirondack Mountains, New York, show that the extent and nature of resetting of isotopic and mineralogic systems is highly variable. There is a strong correlation between retrogression and shearing, and the rocks may be divided texturally into: (1) unsheared lithologies that preserve little-retrogressed pyroxene-or hornblendebearing peak-metamorphic mineralogies; and (2) sheared rocks that underwent retrogression, marked by the growth of late biotite, in centimetre-to metre-wide shear zones after the peak of metamorphism. Oxygen fugacities in the unsheared lithologies were estimated for reintegrated mineral compositions from magnetiteilmenite (Mt-Ilm) and ferrosilite-magnetic-quartz (Fs-Mt-Qtz) equilibria. Mt-Ilm yields logfO2Mt-Ilm values of-15.9 to-17.6 (0.6 to 1.3 log units below the fayalite-magnetite-quartz buffer, FMQ) and temperatures of 670–745°C that agree with those from other geothermometry and phase equilibria studies. These data suggest that, aside from oxyexsolution of ilmenite from magnetite, the Fe-Ti system underwent only minor resetting during cooling, and the Fe-Ti oxides yield good estimates of peak-metamorphic temperatures and fO2. In unsheared ilmenite + magnetite + orthopyroxene + quartz assemblages, values of logfO2Mt-Ilm are lower than logfO2Fs-Mt-Qtz by an average of 0.6 when the orthopyroxene activity model of Sack and Ghiorso is used. Minor resetting of the Fe-Ti oxides, analytical errors, and errors in the placement of end-member reactions probably account for this relatively small difference in fO2 values. Whole-rock δ18O values of unsheared Diana and Stark lithologies range from 4.0 to 10.3‰ reflecting pre-regional metamorphic oxygen-isotope ratios. Peak-metamorphic minerals preserve high-temperature oxygen-isotope fractionations, and, in many samples, the effective diffusion of oxygen in minerals ceased at higher temperatures than predicted from wet experimental diffusion data. These data suggest that the rocks did not contain an aqueous fluid phase during cooling. The combination of petrologic, isotopic, and textural data also permits a detailed study of shearing and retrogression. Ilmenites in the sheared lithologies underwent greater degrees of hematite loss than in the unsheared rocks, resulting in logfO2Mt-Ilm values as low as-24.1 (3.1 log units below FMQ) and Mt-Ilm temperatures that are up to 175°C below regional estimates. Sheared rocks also have higher δ18O values (up to 13.3‰). During shearing, δ18O values of biotite, K-feldspar, and magnetite reset readily, while the degree of isotopic resetting of quartz correlates with the intensity for recrystallization.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Albee AL, Ray L (1970) Correction factors for electron probe microanalysis of silicates, oxides, carbonates, phosphates and sulfates. Anal Chem 42:1408–1414Google Scholar
  2. Anderson DJ, Lindsley DH (1988) Internally consistent solution models for Fe-Mg-Mn-Ti oxides: Fe-Ti oxides. Am Mineral 73:714–726Google Scholar
  3. Barnicoat AC, O'Hara MJ (1979) High temperature pyroxenes from an ironstone at Scourie, Sutherland. Mineral Mag 43:371–375Google Scholar
  4. Bence AE, Albee AL (1968) Empirical correction factors for the electron microanalysis of silicates and oxides. J Geol 76:382–403Google Scholar
  5. Bohlen SR, Essene EJ (1977) Feldspar and oxide thermometry of granulites in the Adirondack Highlands. Contrib Mineral Petrol 62:153–169Google Scholar
  6. Bohlen SR, Essene EJ, Boettcher AL (1980) Reinvestigation and application of olivine-quartz-orthopyroxene barometry. Earth Planet Sci Lett 47:1–10Google Scholar
  7. Bohlen SR, Valley JW, Essene EJ (1985) Metamorphism in the Adirondacks. I. Petrology, pressure and temperature. J Petrol 26:971–992Google Scholar
  8. Bottinga Y, Javoy M (1973) Comments on oxygen isotope geothermometry. Earth Planet Sci Lett 20:251–265Google Scholar
  9. Bottinga Y, Javoy M (1975) Oxygen isotope partitioning among the minerals in igneous and metamorphic rocks. Rev Geophys Space Phys, 13:401–418Google Scholar
  10. Buddington AF, Leonard BF (1962) Regional geology of the St Lawrence County magnetite district, northwest Adirondacks, New York. US Geol Surv Prof Pap 376Google Scholar
  11. Buddington AF, Lindsley DH (1964) Iron-titanium oxide minerals and synthetic equivalents. J Petrol 5:310–357Google Scholar
  12. Burton KW, O'Nions RK (1990) Fe-Ti oxide chronometry: with application to granulite formation. Geochim Cosmochim Acta 54:2593–2602Google Scholar
  13. Cartwright I (1990) Prograde metamorphism, anatexis and retrogression of the Scourian complex, NW Scotland. In: Brown M, Ashworth J (eds) High temperature metamorphism and crustal anatexis. Unwin-Hyman, London, pp 371–399Google Scholar
  14. Cartwright I, Valley JW (1990) Fluid-rock interaction in the NW Adirondack Mountains, New York. In: Brown M, Ashworth J (eds) High temperature metamorphism and crustal anatexis. Unwin-Hyman, London, pp 180–197Google Scholar
  15. Cartwright I, Valley JW (1991) Steep oxygen isotope gradients from marble-metagranite contacts in the northwest Adirondacks: the products of fluid-hosted diffusion. Earth Planet Sci Lett 107:148–163Google Scholar
  16. Cartwright I, Valley JW (1992) Oxygen-isotope geochemistry of the Scourian complex, northwest Scotland. J Geol Soc London 149:115–126Google Scholar
  17. Chiarenzelli JR, McLelland JM (1991) Age and regional relationships of granitoid rocks of the Adirondack Highlands. J Geol 99:571–590Google Scholar
  18. Clayton RN, Mayeda TK (1963) The use of bromine pentafluoride in the extraction of oxygen from oxides and silicates for isotopic analysis. Geochim Cosmochim Acta 27:43–52Google Scholar
  19. Clayton RN, Goldsmith JR, Mayeda TK (1989) Oxygen isotope fractionation in quartz, albite, anorthite, and calcite. Geochim Cosmochim Acta 53:725–733Google Scholar
  20. Connolly C, Muehlenbachs K (1988) Contrasting oxygen diffusion in nepheline, diopside and other silicates and their relevance to isotopic systematics in meteorites. Geochim Cosmochim Acta 52:1585–1591Google Scholar
  21. Criss RE, Taylor HP (1986) Meteroric-hydrothermal systems. In: Valley JW, Taylor HP, O'Neil JR (eds) Stable isotopes in high temperature geological processes. (Reviews in Mineralogy) Mineral Soc Am 16:373–424Google Scholar
  22. Davidson A (1986) New interpretations in the southwestern Grenville Province. In: Moore JM, Baer AJ (eds) The Grenville Province. Geol Assoc Can Spec Pap 31:61–74Google Scholar
  23. Dipple GM, Ferry JM (1992) Metasomatism and fluid flow in ductile fault zones. Contrib Mineral Petrol 112:149–164Google Scholar
  24. Dodson MH (1973) Closure temperature in cooling geochronological and petrological systems. Contrib Mineral Petrol 40:259–274Google Scholar
  25. Eiler JE, Valley JW (1991) Stable isotope characteristics and magmatic history of metaigneous rocks, Adirondacks, NY. EOS, Trans Am Geophys Union 72:310Google Scholar
  26. Eiler JE, Baumgartner LP, Valley JW (1992) Intercrystalline stable isotope diffusion: a fast grain boundary model. Contrib Mineral Petrol 112:543–557Google Scholar
  27. Elphick SC, Graham CM (1988) The effect of hydrogen on oxygen diffusion in quartz: evidence for fast proton transient? Nature 335:243–245Google Scholar
  28. Elphick SC, Graham CM (1990) Hydrothermal oxygen diffusion in diopside at 1 kb, 900–1200°C, a comparison with oxygen diffusion in forsterite, and constraints on oxygen isotope disequilibrium in peridotite nodules. Terra Abstr 2:72Google Scholar
  29. Elphick SC, Graham CM, Dennis PF (1988) An ion microprobe study of anhydrous oxygen diffusion in anorthite: a comparison with hydrothermal data and some geological interpretations. Contrib Mineral Petrol 100:490–495Google Scholar
  30. Essene EJ (1989) The current status of thermobarometry in metamorphic rocks. In: Daly JS, Cliff RA, Yardley BWD (eds) Evolution of metamorphic belts. Geol Soc London Spec Pub 43:1–44Google Scholar
  31. Farver JR (1989) Oxygen self-diffusion in diopside with application to cooling rate determinations. Earth Planet Sci Lett 92:386–396Google Scholar
  32. Farver JR, Giletti BJ (1985) Oxygen diffusion in amphiboles. Geochim Cosmochim Acta 49:1405–1411Google Scholar
  33. Farver JR, Yund RA (1990) The effect of hydrogen, oxygen, and water fugacity on oxygen diffusion in alkali feldspar. Geochim Cosmochim Acta 54:2953–2964Google Scholar
  34. Friedman I, O'Neil JR (1977) Complilation of stable isotope fractionation factors of geochemical interest. US Geol Surv Prof Pap 440-KKGoogle Scholar
  35. Frost Br, Chacko TC (1989) The granulite uncertainty principle. J Petrol 97:435–450Google Scholar
  36. Frost BR, Lindsley DH, Anderson DJ (1988) Fe-Ti oxide-silicate equilibria: assemblages with fayalitic olivine. Am Mineral 73:727–740Google Scholar
  37. Geraghty EP, Isachsen YW, Wright SF (1981) Extent and character of the Carthage-Colton Mylonite Zone, northwest Adirondacks, New York. Tech Rep US Nuclear Reg Comm NUREG/CR-1865Google Scholar
  38. Ghiorso MS, Sack RO (1991) Thermochemistry of the oxide minerals. In: Lindsley DH (ed) Oxide minerals: petrologic and magnetic significance. (Reviews in Mineralogy) Mineral Soc Am 25:221–264Google Scholar
  39. Giletti BJ (1986) Diffusion effects on oxygen isotope temperatures of slowly cooled igneous and metamorphic rocks. Earth Planet Sci Lett 77:218–228Google Scholar
  40. Giletti BJ, Anderson TF (1975) Studies in diffusion-II. Oxygen in phlogopite mica. Earth Planet Sci Lett 28:225–233Google Scholar
  41. Giletti BJ, Yund RA (1984) Oxygen diffusion in quartz. J Geophys Res 89:4039–4046Google Scholar
  42. Giletti BJ, Hess KC (1988) Oxygen diffusion in magnetite. Earth Planet Sci Lett 89:115–122Google Scholar
  43. Giletti BJ, Semet MP, Yund RA (1978) Studies in diffusion III: oxygen in feldspars: an ion microprobe determination. Geochim Cosmochim Acta 42:179–192Google Scholar
  44. Graham CM, Elphick SC (1990) Some experimental constraints on the role of hydrogen in oxygen and hydrogen diffusion and Al-Si interdiffusion in silicates. In: Ganguly J (ed) Diffusion, atomic ordering, and mass transport. Advances in physical geochemistry vol 8. Springer, Berlin Heidelberg New York, pp 248–285Google Scholar
  45. Hargraves RB (1969) A contribution to the geology of the Diana syenite gneiss complex. In: Isachsen YW (ed) Origin of anorthosite and related rocks. NY State Mus Sci Serv Mem 18:343–356Google Scholar
  46. Hazelwood AM (1987) The role of metamorphic fluids in the amphibolite to granulite facies transition, Adirondack Mountains, New York. MSC Thesis, University of Wisconsin-Madison WI, USAGoogle Scholar
  47. Hewitt DA (1978) A redetermination of the fayalite-magnetitequartz equilibrium between 650°C and 850°C. Am J Sci 278:715–724Google Scholar
  48. Kyser TK (1986) Stable isotope variations in the mantle. In: Valley JW, Taylor HP, O'Neil Jr (eds) Stable isotopes in high temperature geological processes. (Reviews in Mineralogy) Mineral Soc Am 16:141–164Google Scholar
  49. Lamb WM, Valley JW (1984) Metamorphism of reduced granulites in low-CO2 vapour-free environment. Nature 312:56–58Google Scholar
  50. Lamb WM, Valley JW (1985) C-O-H fluid calculations and granulite genesis. In: Tobi AC, Touret JLR (eds) The deep Proterozoic crust in the North Atlantic Provinces. Reidel, Dordrecht, Netherlands, pp 119–131Google Scholar
  51. Lasaga AC (1983) Geospeedometry: an extension of geothermometry. In: Saxena SK (eds) Kinetics and equilibrium in mineral reactions. Advances in physical geochemistry vol 3. Springer, Berlin Heidelberg New York, pp 81–114Google Scholar
  52. McCaig AM (1988) Deep fluid circulation in fault zones. Geology 16:867–870Google Scholar
  53. McLelland JM, Isachsen YW (1986) Synthesis of geology of the Adirondack mountains, New York, and their tectonic setting within the southwestern Grenville Province. In: Moore JM, Baer AJ (eds) The Grenville Province. Geol Assoc Can Spec Pap 31:75–94Google Scholar
  54. McLelland JM, Chiarenzelli J, Whitney P, Isachsen Y (1988) U-Pb zircon chronology of the Adirondack Mountains and implications for their geologic evolution. Geology 16:920–924Google Scholar
  55. Mezger K, Rawnsley CM, Bohlen SR, Hanson GN (1991) U-Pb garnet, sphene, monazite, and rutile ages: implications for the duration of high-grade metamorphism and cooling histories, Adirondack Mts., New York. J Geol 99:414–428Google Scholar
  56. Morrison J, Valley JW (1988) Contamination of the Marcy anorthosite massif, Adirondack Mountains, NY: petrologic and isotopic evidence. Contrib Mineral Petrol 98:97–108Google Scholar
  57. Myers J, Eugster HP (1983) The system Fe-Si-O: oxygen buffer calibrations of 1500 K. Contrib Mineral Petrol 82:75–90Google Scholar
  58. Nagy KL, Giletti BJ (1986) Grain boundary diffusion of oxygen in a macroperthitic feldspar. Geochim Cosmochim Acta 50:1151–1158Google Scholar
  59. Newton RC (1986) Fluids of granulite facies metamorphism. In: Walther JV, Wood BJ (eds) Fluid-rock interactions during metamorphism. Springer, New York Berlin Heidelberg, pp 36–59Google Scholar
  60. Newton RC (1992) Charnockitic alteration: evidence for CO2 infiltration in granulite facies metamorphism. J Metamorphic Geol 10:383–400Google Scholar
  61. Newton RC, Hanson EC (1983) The origin of Proterozoic and late Archaean charnockites—evidence from field relations and experimental petrology. Mem Geol Soc Am 161:167–178Google Scholar
  62. O'Hara MJ, Yarwood G (1978) High pressure-temperature point on a Archaean geotherm, implied magma genesis by crustal anatexis and consequences for garnet-pyroxene thermometry and barometry. Philos Trans R Soc London A228:441–456Google Scholar
  63. O'Neil JR, Taylor HP (1967) The oxygen isotope and cation exchange chemistry of feldspars. Am Mineral 52:1414–1437Google Scholar
  64. Perkins D, Chipera SJ (1985) Garnet-orthopyroxene-plagioclasequartz barometry: refinement and application to the English River subprovince and Minnesota River valley. Contrib Mineral Petrol 89:69–80Google Scholar
  65. Peterson DE, Valley JW (1988) Comparison of ideal and non-ideal orthopyroxene activities in alm-fs and pyr-en geobarometry. Geol Soc Am Abstr Progr 20:98Google Scholar
  66. Powers RE, Bohlen SR (1985) The role of synmetamorphic igenous rocks in the metamorphism and partial melting of metasediment, NW Adirondacks. Contrib Mineral Petrol 90:401–409Google Scholar
  67. Robinson GR, Haas JL Jr, Schafer CM, Haselton HT Jr (1983) Thermodynamic and thermophysical properties of selected phases in the MgO-SiO2-H2O-CO2, CaO-Al2O3-SiO2-H2O-CO2, and Fe-FeO-Fe2O3-SiO2 chemical systems, with special emphasis on basalts and their mineral components. US Geol Surv Open-File Rep 83-79Google Scholar
  68. Rollinson HR (1980) Iron-titanium oxides as an indicator of the role of the fluid phase during the cooling of granites metamorphosed to granulite grade. Mineral Mag 43:165–170Google Scholar
  69. Sack RO, Ghiorso MS (1989) Importance of considerations of mixing properties in establishing an internally consistent thermodynamic database: thermochemistry of minerals in the system Mg2SiO4-Fe2SiO4-SiO2. Contrib Mineral Petrol 102:41–68Google Scholar
  70. Sharp ZD, O'Neil JR, Essene EJ (1988) Oxygen isotope variations in granulite-grade iron formations: constraints on oxygen diffusion and retrograde isotopic exchange. Contrib Mineral Petrol 98:490–501Google Scholar
  71. Taylor HP, Sheppard SMF (1986) Igenous rocks: I Process of isotopic fractionation and isotope systematics. In: Valley JW, Taylor HP, O'Neil JR (eds) Stable isotopes in high temperature geological processes. (Reviews in Mineralogy) Mineral Soc 16:227–272Google Scholar
  72. Valley JW (1985) Polymetamorphism in the Adirondacks: wollastonite at contacts of shallowly intruded anorthosite. In: Tobi AC, Touret JLR (eds) The deep proterozoic crust in the North Atlantic Provinces. Reidel, Dordrecht, Netherlands, pp 217–235Google Scholar
  73. Valley JW (1992) Granulite formation is driven by magmatic processes in the deep crust. Earth-Sci Rev 32:145–146Google Scholar
  74. Valley JW, Essene EJ (1980) Calc-silicate reactions in Adirondack marbles: the role of fluids and solid solutions. Geol Soc Am Bull 91:114–117, 720–815Google Scholar
  75. Valley JW, O'Neil JR (1982) Oxygen isotope evidence for shallow emplacement of Adirondack anorthosite. Nature 300:497–500Google Scholar
  76. Valley JW, O'Neil JR (1984) Fluid heterogeneity during granulite facies metamorphism in the Adirondacks: stable isotope evidence. Contrib Mineral Petrol 85:158–173Google Scholar
  77. Valley JW, Graham CM (1991) Ion microprobe analysis of oxygen isotope ratios in granulite facies magnetites: diffusive exchange as a guide to cooling history. Contrib Mineral Petrol 109:38–52Google Scholar
  78. Wood BJ, Banno S (1973) Garnet-orthopyroxene and orthopyroxene-clinopyroxene relationships in simple and complex systems. Contrib Mineral Petrol 42:109–124Google Scholar

Copyright information

© Springer-Verlag 1993

Authors and Affiliations

  • Ian Cartwright
    • 1
  • John W. Valley
    • 2
  • Anne-Marie Hazelwood
    • 2
  1. 1.Victorian Institute of Earth and Planetary Sciences, Department of Earth SciencesMonash UniversityClaytonAustralia
  2. 2.Department of Geology and GeophysicsUniversity of WisconsinMadisonUSA
  3. 3.EvansvilleUSA

Personalised recommendations