Distribution of ferric iron in some upper-mantle assemblages

The distribution of ferric iron among the phases of upper-mantle rocks, as a function of pressure (P), temperature (T) and bulk composition, has been studied using Fe-57 Mossbauer spectroscopy to determine the Fe3+/Sigma Fe ratios of mineral separates from 35 peridotite and pyroxenite samples. The whole-rock Fe3+ complement of a peridotite is typically shared approximately evenly among the major anhydrous phases (spinel and/or garnet, orthopyroxene and clinopyroxene), with the important exception of olivine, which contains negligible Fe3+. Whole-rock Fe3+ contents are independent of the T and P of equilibration of the rock, but show a well-defined simple inverse correlation with the degree of depletion in a Basaltic component. Fe3+ in spinel and in both pyroxenes from the spinel lherzolite facies shows a positive correlation with temperature, presumably owing to the decrease in the modal abundance of spinel. In garnet peridotites, the Fe3+ in garnet increases markedly with increasing T and P, whereas that in clinopyroxene remains approximately constant. The complex nature of the partitioning of Fe3+ between mantle phases results in complicated patterns of the activities of the Fe3+-bearing components, and thus in calculated equilibrium f(O2), which show little correlation with whole-rock Fe3+ or degree of depletion. Whether Fe3+ is taken into account or ignored in calculating mineral formulae for geothermobarometry can have major effects on the resulting calculated T and P. For Fe-Mg exchange geothermometers, large errors muse occur when applied to samples more oxidized or reduced than the experimental calibrations, whose f(O2) conditions are largely unknown. Two-pyroxene thermometry is more immune to this problem and probably provides the most reliable P-T estimates Accordingly, the convergence of P-T values derived for a given garnet peridotite assemblage may not necessarily be indicative of mineral equilibrium. The prospects for the calculation of accurate Fe3+ contents from electron microprobe analyses by assuming stoichiometry are good for spinel, uncertain for garnet, and distinctly poor for pyroxenes.