Contributions to Mineralogy and Petrology

, Volume 107, Issue 1, pp 27–40 | Cite as

High pressure experimental calibration of the olivine-orthopyroxene-spinel oxygen geobarometer: implications for the oxidation state of the upper mantle

  • C. Ballhaus
  • R. F. Berry
  • D. H. Green


Synthetic spinel harzburgite and lherzolite assemblages were equilibrated between 1040 and 1300° C and 0.3 to 2.7 GPa, under controlled oxygen fugacity (fO2). fO2 was buffered with conventional and open double-capsule techniques, using the Fe−FeO, WC-WO2-C, Ni−NiO, and Fe3O4−Fe2O3 buffers, and graphite, olivine, and PdAg alloys as sample containers. Experiments were carried out in a piston-cylinder apparatus under fluid-excess conditions. Within the P-T-X range of the experiments, the redox ratio Fe3+/ΣFe in spinel is a linear function of fO2 (0.02 at IW, 0.1 at WCO, 0.25 at NNO, and 0.75 at MH). It is independent of temperature at given Δlog(fO2), but decreases slightly with increasing Cr content in spinel. The Fe3+/ΣFe ratio falls with increasing pressure at given Δlog(fO2), consistent with a pressure correction based on partial molar volume data. At a specific temperature, degree of melting and bulk composition, the Cr/(Cr+Al) ratio of a spinel rises with increasing fO2. A linear least-squares fit to the experimental data gives the semi-empirical oxygen barometer in terms of divergence from the fayalite-magnetite-quartz (FMQ) buffer:
$$\Delta log (f_{O_2 } )^{FMQ} = 0.27 + 2505/T - 400P/T - 6 log(X_{Fe}^{olv} ) - 3200(1 - X_{Fe}^{olv} )^2 /T + 2 log(X_{Fe^{2 + } }^{sp} ) + 4 log(X_{Fe^{3 + } }^{sp} ) + 2630(X_{Al}^{sp} )^2 /T.$$

The oxygen barometer is applicable to the entire spectrum of spinel compositions occurring in mantle rocks and mantle-derived melts, and gives reasonable results to temperatures as low as 800° C.


Olivine Oxygen Fugacity Partial Molar Volume Pressure Correction Redox Ratio 
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.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Arculus RJ (1978) Mineralogy and petrology of Grenada, Lesser Antilles Island Arc. Contrib Mineral Petrol 65:413–424CrossRefGoogle Scholar
  2. Arculus RJ (1985) Oxidation status of the mantle: past and present. Ann Rev Earth Planet Sci 13:75–95Google Scholar
  3. Arculus RJ, Wills KJA (1980) The petrology of plutonic blocks and inclusions from the Lesser Antilles island arc. J Petrol 21:743–799Google Scholar
  4. Ayuso RA, Bence AE, Taylor SR (1976) Upper Jurassic tholeiitic basalts from DSDP Leg 11. J Geophys Res 81:4305–4325Google Scholar
  5. Ballhaus C, Berry RF, Green DH (1990) Oxygen fugacity controls in the Earth's upper mantle. Nature 349:437–440Google Scholar
  6. Barron LM, Slansky E, Suppel D, Johan Z, Ohnenstetter M (1990) Late-to post-magmatic PGE mineralisation in the Fifield platinum province and the Owendale Intrusive Complex, NSW (abstract). 10th Australian Geological Congress, Geol Soc Austr, pp 132Google Scholar
  7. Barsdell M, Berry RF (1990) Origin and evolution of primitive island are ankaramites from Western Epi, Vanuatu. J Petrol 31:747–777Google Scholar
  8. Batiza R, Vanko D (1984) Petrology of young Pacific seamounts. J Geophys Res 89:11235–11260Google Scholar
  9. Berman RG (1988) Internally-consistent thermodynamic data for minerals in the system K2O−Na2O−CaO−MgO−FeO−Fe2O3−Al2O3−SiO2−TiO2−H2O−CO2. J Petrol 29: 445–522Google Scholar
  10. Brearley M, Scarfe CM, Fujii T (1984) The petrology of ultramafic xenoliths from Summit Lake, near Prince George, British Columbia. Contrib Mineral Petrol 88:53–63CrossRefGoogle Scholar
  11. Bryan WB, Thompson G, Ludden JN (1981) Compositional variation in normal MORB from 22°–25°N: Mid-Atlantic ridge and Kane fracture zone. J Geophys Res 86:11815–11836Google Scholar
  12. Bryndzia LT, Wood BJ, Dick HJB (1989) The oxidation state of the Earth's sub-oceanic mantle from oxygen thermobarometry of abyssal peridotites. Nature 341:526–527CrossRefGoogle Scholar
  13. Canil D, Virgo D, Scarfe CM (1990) Oxidation state of mantle xenoliths from British Columbia, Canada. Contrib Mineral Petrol 104:453–462CrossRefGoogle Scholar
  14. Carmichael ISE, Ghiorso MS (1986) Oxidation-reduction relations in basic magmas: a case for homogeneous equilibria. Earth Planet Sci Lett 78:200–210CrossRefGoogle Scholar
  15. Carroll MR, Rutherford MJ (1987) The stability of igneous anhydrite: experimental results and implications for sulfur behavior in the 1982 El Chichon trachyandesite and other evolved magmas. J Petrol 28:781–801Google Scholar
  16. Christie DM, Carmichael ISE, Langmuir CH (1986) Oxidation states of mid-ocean ridge basalt glasses. Earth Planet Sci Lett 79:397–411CrossRefGoogle Scholar
  17. Conrad WK, Kay RW (1984) Ultramafic and mafic inclusions from Adak Island: crystallization history, and implications for the nature of primary magmas and crustal evolution in the Aleutian arc. J Petrol 25:88–125Google Scholar
  18. Davis AS, Clague DA (1987) Geochemistry, mineralogy, and petrogenesis of basalt from the Gorda Ridge. J Geophys Res 92:10467–10483Google Scholar
  19. Dawson JB, Smith JV (1988) Metasomatized and veined uppermantle xenoliths from Pello Hill, Tanzania: Evidence for anomalously-light mantle beneath the Tanzanian sector of the East African Rift Valley. Contrib Mineral Petrol 100:510–527CrossRefGoogle Scholar
  20. Della Giusta A, Princivalle F, Carbonin S (1986) Crystal chemistry of natural Cr-bearing spinels with 0.15≦Cr≦1.07. Neues Jahrb Mineral Abh 155:319–330Google Scholar
  21. DeBari S, Kay SM, Kay RW (1987) Ultramafic xenoliths from Adagdak volcano, Adak, Aleutian island, Alaska: deformed igneous cumulates from the MOHO of an island arc. J Geol 95:329–341Google Scholar
  22. Dick HJB (1989) Abyssal peridotites, very slow spreading ridges and oceanic ridge magmatism. In: Saunders AD, Norry MJ (eds) Magmatism in oceanic basins. Geol Soc Spec Publ 42, Blackwell, Oxford, pp 71–105Google Scholar
  23. Dick HJB, Bryan WB (1978) Variation of basalt phenocryst mineralogy and rock compositions in DSDP hole 396B. Init Rep DSDP 46:215–224Google Scholar
  24. Dick HJB, Bullen T (1984) Chromian spinel as petrogenetic indicator in abyssal and alpine-type periodotites and spatially associated lavas. Contrib Mineral Petrol 86:54–76CrossRefGoogle Scholar
  25. Dungan MA, Long PE, Rhodes JM (1979) The petrography, mineral chemistry, and one-atmosphere phase relations of basalts from site 395. Init Rep DSDP 45:461–472Google Scholar
  26. Dyar MD, McGuire AV, Ziegler RD (1989) Redox equilibria and crystal chemistry of coexisting minerals from spinel lherzolite mantle xenoliths. Am Mineral 74:969–980Google Scholar
  27. Eggler DH (1983) Upper mantle oxidation state: evidence from olivine-orthopyroxene-ilmenite assemblages. Geophys Res Lett 10:365–368Google Scholar
  28. Evans BW, Frost BR (1975) Chrome-spinel in progressive metamorphism — a preliminary analysis. Geochim Cosmochim Acta 39:959–972CrossRefGoogle Scholar
  29. Fabriès J (1979) Spinel-olivine geothermometry in peridotites from ultramafic complexes. Contrib Mineral Petrol 69:329–336CrossRefGoogle Scholar
  30. Falloon TJ, Green DH (1987) Anhydrous partial melting of MORB pyrolite and other periodotite compositions at 10 kb: implications for the origin of primitive MORB glasses. Mineral Petrol 37:181–219CrossRefGoogle Scholar
  31. Fisk MR, Bence AE (1980) Experimental crystallization of chrome spinel in FAMOUS basalt 527-1-1. Earth Planet Sci Lett 48:111–123CrossRefGoogle Scholar
  32. Francis D (1987) Mantle-melt interaction recorded in spinel lherzolite xenoliths from the Alligator Lake volcanic complex, Yukon, Canada. J Petrol 28:569–597Google Scholar
  33. Fujii T, Scarfe CM (1982) Petrology of ultramafic nodules from West Kettle River, near Kelowna, sourthern British Columbia. Contrib Mineral Petrol 80:297–306CrossRefGoogle Scholar
  34. Furnes H, Pedersen RB, Maaløe S (1986) Petrology and geochemistry of spinel peridotite nodules and host basalt, Vestspitsbergen. Nor Geol Tiddskr 66:53–68Google Scholar
  35. Furuta T, Tokuyama H (1983) Chromian spinels in Costa Rica basalts, Deep Sea Drilling Project site 505-a preliminary interpretation of electron microprobe analyses. Init Repts DSDP 69:805–811Google Scholar
  36. Ghiorso MS, Carmichael ISE (1988) Modelling magmatic systems: petrologic applications. In: Carmichael, ISE, Eugster HP (eds) Thermodynamic modelling of geological materials: Minerals, fluids and melts. Reviews in Mineralogy, vol 17. Mineral Soc Am, pp 467–499Google Scholar
  37. Green DH, Ringwood AE (1967) The genesis of basaltic magmas. Contrib Mineral Petrol 15:103–190CrossRefGoogle Scholar
  38. Green DH, Wallace ME (1988) Mantle metasomatism by ephemeral carbonatite melts. Nature 336:459–462CrossRefGoogle Scholar
  39. Green DH, Hibberson WO, Jaques AL (1979) Petrogenesis of midocean ridge basalts. In: McElhinney MW (ed) The earth: Its origin, structure, and evolution. Acad Press, London, pp 265–299Google Scholar
  40. Green DH, Falloon TJ, Taylor WR (1987) Mantle-derived magmas-roles of variable source peridotite and variable C−H−O fluid compositions. In: Mysen BO (ed) Magmatic processes. Physicochemical principles. Geochem Soc, London, pp 139–154Google Scholar
  41. Grove TL (1981) Use of FePt alloys to eliminate the iron loss problem in 1 atmosphere gas mixing experiments: theoretical and practical considerations. Contrib Mineral Petrol 78:298–304Google Scholar
  42. Gutmann JT (1986) Origin of four-and five-phase ultramafic xenoliths from Sonora, Mexico. Am Mineral 71:1076–1084Google Scholar
  43. Haggerty SE (1979) Spinels in high pressure regimes. In: Boyd FR, Meyer HOA (eds) The mantle sample:Inclusions in kimberlites and other volcanics. 2nd Intern. Kimberlite Conf Santa Fe, pp 183–196Google Scholar
  44. Haggerty SE (1986) Diamond genesis in a multiply-constrained model. Nature 320:34–39CrossRefGoogle Scholar
  45. Hill RET, Roeder PL (1974) The crystallization of spinel from basaltic liquid as a function of oxygen fugacity. J Geol 82:709–729Google Scholar
  46. Huebner JS (1971) Buffering techniques for hydrostatic systems at elevated pressures. In: Ulmer GC (ed) Research techniques for high pressure and high temperatures. Springer, Berlin Heidelberg New York, pp 123–177Google Scholar
  47. Irvine TN (1967) Chromian spinel as petrogenetic indicator. Part 2. Petrologic applications. Can J Earth Sci 4:71–103Google Scholar
  48. Irvine TN (1973) Bridget Cove volcanics, Juneau Area, Alaska: Possible parental magma of Alaskan-type ultramafic complexes. Carnegie Inst Washington Yearb 72:478–491Google Scholar
  49. Jaques AL, Green DH (1980) Anhydrous melting of peridotite at 0–15 kbar pressure and the genesis of tholeiitic basalts. Contrib Mineral Petrol 73:287–310CrossRefGoogle Scholar
  50. Jarosewich E, Nelen JA, Norberg JA (1980) References samples for electron microprobe analysis. Geostand Newslett 4:43–47Google Scholar
  51. Johnson RW, Jaques AL, Hickey RL, McKee CO, Chappell BW (1985) Manam Island, Papua New Guinea: Petrology and geochemistry of a low-TiO2 basaltic island-arc volcano. J Petrol 26:283–323Google Scholar
  52. Jones AP, Smith JV, Dawson JB (1983) Glasses in mantle xenoliths from Olmani, Tanzania. J Geol 91:167–178Google Scholar
  53. Kesson SE, Ringwood AE (1989) Slab-mantle interactions 2. The formation of diamonds. Chem Geol 78:97–118Google Scholar
  54. Koch-Mueller M, Cemic L, Langer K (1989) An experimental study of orthopyroxene=olivine+quartz equilibria (Abstr.). Terra Abstracts 1:140Google Scholar
  55. Kurat G, Palme H, Spettel B, Baddenhausen H, Hofmeister H, Palme C, Wänke H (1980) Geochemistry of ultramafic xenoliths from Kapfenstein Austria: evidence from a variety of upper mantle processes. Geochim Cosmochim Acta 44:45–60CrossRefGoogle Scholar
  56. Kyser TK, O'Neil JR, Carmichael ISE (1981) Oxygen isotope thermometry of basic lavas and mantle nodules. Contrib Mineral Petrol 77:11–23CrossRefGoogle Scholar
  57. le Roex AP (1987) Source regions of mid-ocean ridge basalts: evidence for enrichment processes. In: Menzies MA, Hawkesworth CJ (eds) Mantle metasomatism. Acad Press London, pp 389–421Google Scholar
  58. Lindsley DH (1976) The crystal chemistry and structure of oxide minerals as examplified by the Fe−Ti oxides. In: Rumble III D (ed) Oxide Minerals. Reviews in Mineralogy, vol 3. Miner Soc Am, pp L1–L60Google Scholar
  59. Lucas H, Muggeridge MT, McConchie DM (1988) Iron in kimberlitic ilmenites and chromian spinels: a survey of analytical techniques. In: Ross J (ed) Kimberlites and related rocks: 4th Intern Kimberlite Conf Perth, pp 311–320Google Scholar
  60. Mattioli GS, Wood BJ (1988) Magnetite activities across the MgAl2O4−Fe3O4 spinel join, with application to thermobarometric estimates of upper mantle oxygen fugacity. Contrib Mineral Petrol 98:148–162CrossRefGoogle Scholar
  61. Mattioli GS, Baker MB, Rutter MJ, Stolper EM (1989) Upper mantle oxygen fugacity and its relationship to metasomatism. J Geol 97:521–536Google Scholar
  62. McGuire AV, Dyar MD, Ward KA (1989) Neglected Fe3+/Fe2+ ratios: a study of Fe3+ content of megacrysts from alkali basalts. Geology 17:687–690CrossRefGoogle Scholar
  63. Murck BW, Campbell IH (1986) The effects of temperature, oxygen fugacity and melt composition on the behaviour of chromium in basic and ultrabasic melts. Geochim Cosmochim Acta 50:1871–1887CrossRefGoogle Scholar
  64. Natland JH (1989) Partial melting of a lithologically heterogeneous mantle: inferences from crystallization histories of magnesian abyssal tholeiites from the Siqueiros Facture Zone. In: Saunders AD, Norry MJ (eds) Magmatism in the ocean basins. Geol Soc Spec Publ 42, Blackwell, Oxford, pp 41–70Google Scholar
  65. Natland JH, Adamson AC, Laverne C, Melson WG, O'Hearn T (1983) A compositionally nearly steady-state magma chamber at the Costa Rica rift: evidence from basalt glass and mineral data. Init Rep DSDP 69:811–858Google Scholar
  66. Neumann ER, Schilling JG (1984) Petrology of basalts from the Mohns-Knipovich ridge; the Norwegian-Greenland sea. Contrib Mineral Petrol 85:209–223CrossRefGoogle Scholar
  67. Nixon GT, Cabri LJ, Laflamme JHG (1989) Provenance of platinum nuggets in Tulameen placer deposits (abstract). Bull Geol Soc Finl 61 (5th Intern Platinum Conf): 45Google Scholar
  68. Nye CJ, Reid MR (1986) Geochemistry of primary and least fractionated lavas from Okmok volcano, central Aleutians: implications for arc magmagenesis. J Geophys Res 91:10271–10287Google Scholar
  69. Nye CJ, Turner DL (1990) Petrology, geochemistry, and age of the Spurr volcanic complex, eastern Aleutian arc. Bull Volcanol 52:205–226CrossRefGoogle Scholar
  70. O'Neill HStC (1987a) The quartz-fayalite-iron and quartz-fayalitemagnetite equilibria and the free energies of formation of fayalite (Fe2SiO4) and magnetite (Fe3O4). Am Mineral 72:67–75Google Scholar
  71. O'Neill HStC (1987b) The free energies of formation of NiO, CoO, Ni2SiO4. Am Mineral 72:280–291Google Scholar
  72. O'Neill HStC, Navrotsky A (1984) Cation distributions and thermodynamic properties of binary spinel solid solutions. Am Mineral 69:733–753Google Scholar
  73. O'Neill HStC, Wall VJ (1987) The olivine-orthopyroxene-spinel oxygen geobarometer, the nickel precipitation curve, and the oxygen fugacity of the Earth's upper mantle. J Petrol 28:1169–1191Google Scholar
  74. Preß S, Witt G, Seck HA, Eonov D, Kovalenko VL (1986) Spinel peridotite xenoliths from the Tariat depression, Mongolia. I: Major element chemistry and mineralogy of a primitive mantle xenolith suite. Geochim Cosmochim Acta 50:2587–2599Google Scholar
  75. Ramsay WRH, Crawford AJ, Foden JD (1984) Field setting, mineralogy, chemistry and genesis of arc picrites, New Georgia, Solomon Islands. Contrib Mineral Petrol 88:386–402CrossRefGoogle Scholar
  76. Reid AM, Donaldson CH, Brown RW, Ridley WI, Dawson JB (1975) Mineral chemistry of peridotite xenoliths from the Lashaine volcano, Tanzania. Phys Chem Earth 9:525–543Google Scholar
  77. Roeder PL, Campbell IH, Jamieson H (1979) A re-evaluation of the olivine-spinel geothermometer. Contrib Mineral Petrol 68:325–334Google Scholar
  78. Sachtleben T, Seck HA (1980) Chemical control on Al solubility in orthopyroxene, and its implications on pyroxene geothermometry. Contrib Mineral Petrol 78:157–165Google Scholar
  79. 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 102:41–68CrossRefGoogle Scholar
  80. Schwab RG, Küstner D (1981) Die Gleichgewichtsfugazitäten technologisch und petrologisch wichtiger Sauerstoffpuffer. Neues Jahrb Mineral Abh 140:111–142Google Scholar
  81. Sigurdsson H (1977) Spinels in Leg 37 basalts and peridotites: phase chemistry and zoning. Init Rep DSDP 37:883–891Google Scholar
  82. Sigurdsson H, Schilling JG (1976) Spinels in mid-Atlantic ridge basalts: chemistry and occurrence. Earth Planet Sci Lett 29:7–20CrossRefGoogle Scholar
  83. Tatsumi Y, Ishizaka K (1982) Magnesian andesite and basalt from Shodo-shima island, southwest Japan, and their bearing on the genesis of calc-alkaline andesites. Lithos 15:161–172CrossRefGoogle Scholar
  84. Taylor WR, Foley SF (1989) Improved oxygen-buffering techniques for C−O−H fluid-saturated experiments at high pressure. J Geophys Res 94:4146–4158Google Scholar
  85. Taylor WR, Green DH (1987) Measurement of reduced peridotite-C−O−H solidus and implications for redox melting of the mantle. Nature 332:349–352Google Scholar
  86. Thy P (1983) Spinel minerals in transitional and alkali basaltic glasses from Iceland. Contrib Mineral Petrol 83:141–149CrossRefGoogle Scholar
  87. Wallace ME, Green DH (1988) An experimental determination of primary carbonatite magma compostion. Nature 335:343–346CrossRefGoogle Scholar
  88. Winterburn PA, Harte B, Gurney JJ (1990) Peridotite xenoliths from the Jagersfontein kimberlite pipe: I. Primary and primary-metasomatic mineralogy. Geochim Cosmochim Acta 54:329–341CrossRefGoogle Scholar
  89. Wood BJ, Virgo D (1989) Upper mantle oxidation state: ferric iron contents of lherzolite spinels by 57Fe Mössbauer spectroscopy and resultant oxygen fugacities. Geochim Cosmochim Acta 53:1277–1291Google Scholar

Copyright information

© Springer-Verlag 1991

Authors and Affiliations

  • C. Ballhaus
    • 1
  • R. F. Berry
    • 1
  • D. H. Green
    • 1
  1. 1.Geology DepartmentUniversity of TasmaniaHobartAustralia

Personalised recommendations