Abstract
We have determined the equilibrium Fe2+–Mg fractionation between orthopyroxene and spinel in the ferromagnesium system at 0.9–1.4 GPa, 850–1,250 °C, and also as a function of the Cr/Al ratio of spinel at 1.24 GPa, 1,000 °C. At each P–T condition, the equilibrium value of the distribution coefficient, KD(Fe–Mg), was constrained by experiments with crystalline starting mixtures, and approaching from both higher and lower initial values. The experimental data have been cast, within a thermodynamic framework, in the form of a geothermometer in the system FeO–MgO–Al2O3–Cr2O3–SiO2 (FMACrS). Using the data of O'Neill and Wall (1987) on the thermodynamic properties of Fe3+ and Ti4+ bearing spinels, we extended the thermometric formulation to account for the effect of these components. However, practical application of the extended formulation is beset with the problem of accurate determination of Fe3+ content of natural minerals. Using published data, the thermometric formulation in the FMACrS system has been applied to a number of natural assemblages that have small Fe3+ content. The retrieved temperatures are generally higher, on the average by ~60 °C, than those obtained from the olivine-spinel Fe2+–Mg exchange thermometer of O'Neill and Wall, as modified by Ballhaus et al. (1991), but are more compatible with the original temperature estimates by the authors of the publications. The smaller Fe2+–Mg interdiffusion coefficient, D(Fe–Mg), in orthopyroxene compared with those in both olivine and spinel is expected to yield higher temperatures from orthopyroxene–spinel than from olivine–spinel thermometry.
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References
Ballhaus C, Berry RF, Green DH (1991) High pressure experimental calibration of the olivine–orthopyroxene–spinel oxygen geobarometer: implications for the oxidation state of the upper mantle. Contrib Mineral Petrol 107:27–40
Berman RG, Aranovich LY (1996) Optimized standard state and solution properties of minerals I. Model calibration for olivine, orthopyroxene, cordierite, garnet, and ilmenite in the system FeO–MgO–CaO–Al2O3–TiO2–SiO2. Contrib Mineral Petrol 126:1–24
Bose K, Ganguly J (1995) Quartz–coesite transition revisited: Reversed experimental determination at 500–1,200 °C and retrieved thermochemical properties. Am Mineral 80:231–238
Chakraborty S (1997) Rates and mechanisms of Fe–Mg interdiffusion in olivine at 980o–1,300 °C. J Geophys Res 102:12317–12331
Engi M (1983) Equilibria involving Al–Cr spinel: Mg–Fe exchange with olivine. Experimental thermodynamic analysis, and consequences for geothermometry. Am J Sci 238-A:29–71
Evans BW, Frost BR (1975) Chrome–spinel in progressive metamorphism—a preliminary analysis. Geochim Cosmochim Acta 39:959–972
Fabries J (1979) Spinel–olivine geothermometer in peridotites from ultramafic complexes. Contrib Mineral Petrol 69:329–336
Førland T (1964) Thermodynamic properties of fused salt systems. In: Sundheim BR (ed) Fused salts. McGraw–Hill, New York, pp 63–164
Fujii T (1978) Fe–Mg partitioning between olivine and spinel. Carnegie Inst Wash Yearbook 76:563–569
Ganguly J, Saxena S (1987) Mixtures and mineral Reactions. Springer, Berlin Heidelberg New York
Ganguly J, Tazzoli V (1994) Fe2+–Mg interdiffusion in orthopyroxene: Retrieval from the data on intracrystalline exchange reaction. Am Mineral 79:930–937
Ganguly J, Bhattacharya RN, Chakraborty S (1988) Convolution effect in the determination of compositional profiles and diffusion coefficients by microprobe step scans. Am Mineral 73:901–909
Gessmann CK, Spiering B, Raith M (1997) Experimental study of the Fe–Mg exchange between garnet and biotite: constraints on the mixing behavior and analysis of the cation-exchange mechanisms. Am Mineral 82:1225–1240
Girod M, Dautria JM, de Giovanni R (1981) A first insight into the constitution of upper mantle under the Hoggar area (southern Algeria): The lherzolite xenoliths in the alkali-basalt. Contrib Mineral Petrrol 77:66–73
Green DH, Ringwood AE, Ware NG, Hibberson WO (1972) Experimental petrology and petrogenesis of Apollo 14 basalt. Proceedings of the 3rd Lunar Science Conference, pp 197–206
Hollister LS (1982) Metamorphic evidence for rapid (2 mm/yr) uplift of a portion of the central-gneiss-complex, coast mountains, BC. Can Mineral 20:319–332
Jamieson HE, Roeder PL (1984) The distribution of Mg and Fe2+ between olivine and spinel at 1,300 °C. Am Mineral 69:238–291
Kertz R (1994) Metamorphic crystallization. Wiley, Chichester
Lee HY, Ganguly J (1987) Equilibrium composition of coexisting garnet and orthopyroxene: experimental determination in the system FeO–MgO–Al2O3–SiO2, and applications. J Petrol 29:93–113
Liermann HP, Ganguly J (2001) Compositional properties of coexisting orthopyroxene and spinel in some Antarctic diogenites: implications for thermal history. Meteor Planet Sci 36:155–166
Liermann HP, Ganguly J (2002) Diffusion coefficients of Fe2+ and Mg in aluminous spinel: experimental determination and applications to terrestrial and planetary problems. Geochim Cosmochim Acta 66:2903–2913
Mori T (1977) Geothermometry of spinel Lherzolites. Contrib Mineral Petrol 59:261–279
Mukherjee AB, Viswanath MT (1987) Thermometry of diogenites. Mem Natl Inst Polar Res, Spec Issue 46:205–215
Mukherjee AB, Bulatov V, Kotelnikov A (1990) New high P–T experimental results on orthopyroxene–chrome spinel equilibrium and a revised orthopyroxene-spinel cosmothermometer. Proc Lunar Planet Sic Conf XX:299–308
Obata M (1980) The Ronda peridotite: garnet-, spinel-, and plagioclase-lherzolite facies and the P–T trajectories of a high-temperature mantle intrusion. J Petrol 21:533–572
O'Neill HSC, Wall VJ (1987) The olivine–spinel oxygen geobarometer, the nickel precipitation curve, and the oxygen fugacity of the Earth's upper mantle. J Petrol 6:1169–1191
Pattison RM (1994) Are reversed Fe–Mg exchange and solid solution experiments really reversed? Am Mineral 79:938–950
Roeder PL, Campbell IH, Jamieson HE (1979) A re-evaluation of the olivine–spinel geothermometer. Contrib Mineral Petrol 68:325–334
Sack RO, Ghiorso SG (1991) Chromian spinel as petrogenetic indicator: thermodynamics and petrological applications. Am Mineral 76:827–847
Saxena SK, Chatterjee N, Fei Y, Shen G (1993) Thermodynamic data on oxides and silicates. Springer, Berlin, Heidelberg, New York
Shervais J (1979) Thermal emplacement model for the Alpine lherzolite Massif at Balmuccia, Italy. J Petrol 20:795–820
Sobolev VN, McCammon CA, Taylor LA, Snyder GA, Sobolev NV (1999) Precise Mössbauer milliprobe determination of ferric iron in rock forming minerals and limitations of electron microprobe analysis. Am Mineral 84:78–85
Truckenbrodt J, Ziegenbein D, Johannes W (1997) Redox conditions in piston-cylinder apparatus: the different behavior of boron nitride and unfired pyrophyllite assemblies. Am Mineral 82:337–344
Wood BJ, Nicholls J (1978) The thermodynamic properties of reciprocal solid solutions. Contrib Mineral Petrol 66:389–400
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 53:1277–1291
Acknowledgements
This research was supported by a NASA grant no. NAG5-10486. We are grateful to Prof. Hans Annersten for the Mössbauer analyses of the spinel samples, and to Prof. Lincoln Hollister for donation of granulite sample from which the orthopyroxene sample, HO, was separated. Drs. Peter Roeder and Martin Engi provided critical, but constructive reviews that led to significant modifications of the paper. J.G. acknowledges the hospitality of the CeSMEC, Florida International University.
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Editorial responsibility: T.L. Grove
An erratum to this article is available at http://dx.doi.org/10.1007/s00410-007-0204-x.
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Liermann, H.P., Ganguly, J. Fe2+–Mg fractionation between orthopyroxene and spinel: experimental calibration in the system FeO–MgO–Al2O3–Cr2O3–SiO2, and applications. Contrib Mineral Petrol 145, 217–227 (2003). https://doi.org/10.1007/s00410-003-0444-3
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DOI: https://doi.org/10.1007/s00410-003-0444-3