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Distribution of Ferric Iron in some Upper-Mantle Assemblages
Authors:CANIL  DANTE; O'NEILL  HUGH ST C
Institution:BAYERISCHES GEOINSTITUT, UNIVERSITAT BAYREUTH D-95440 BAYREUTH, GERMANY
Abstract:The distribution of ferric iron among the phases of upper-mantlerocks, as a function of pressure (P), temperature (T) and bulkcomposition, has been studied using 57Fe Mssbauer spectroscopyto determine the Fe3+/{Sigma}Fe ratios of mineral separates from 35peridotite and pyroxenite samples. The whole-rock Fe3+ complementof a peridotite is typically shared approximately evenly amongthe major anhydrous phases (spinel and/or garnet, orthopyroxeneand clinopyroxene), with the important exception of olivine,which contains negligible Fe3+. Whole-rock Fe3+ contents areindependent of the T and P of equilibration of the rock, butshow a well-defined simple inverse correlation with the degreeof depletion in a basaltic component. Fe3+ in spinel and inboth pyroxenes from the spinel Iherzolite facies shows a positivecorrelation with temperature, presumably owing to the decreasein the modal abundance of spinel. In garnet peridotites, theFe3+ in garnet increases markedly with increasing T and P, whereasthat in clinopyroxene remains approximately constant. The complexnature of the partitioning of Fe3+ between mantle phases resultsin complicated patterns of the activities of the Fe3+ -bearingcomponents, and thus in calculated equilibrium fO2, which showlittle correlation with whole-rock Fe3+ or degree of depletion.Whether Fe3+ is taken into account or ignored in calculatingmineral formulae for geothermobarometry can have major effectson the resulting calculated T and P. For Fe-Mg exchange geothermometers,large errors must occur when applied to samples more oxidizedor reduced than the experimental calibrations, whose fO2 conditionsare largely unknown. Two-pyroxene thermometry is more immuneto this problem, and probably provides the most reliable P—Testimates. Accordingly, the convergence of P—T valuesderived for a given garnet peridotite assemblage may not necessarilybe indicative of mineral equilibrium. The prospects for thecalculation of accurate Fe3+ contents from electron microprobeanalyses by assuming stoichiometry are good for spinel, uncertainfor garnet, and distinctly poor for pyroxenes. KEY WORDS: mantle; oxidation; partitioning; peridotite; thermobarometry *Corresponding author. Present address: School of Earth and Ocean Sciences, University of Victoria, P.O. Box 1700, Victoria, B.C., V8W 2Y2, Canada
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