Abstract: We evaluate the application of 57Fe Mössbauer spectroscopy to the determination of the composition of magnetite (Fe3O4)/maghemite (?-Fe2O3) mixtures and the stoichiometry of magnetite-maghemite solid solutions. In particular, we consider a recently proposed model-independent method which does not rely on a priori assumptions regarding the nature of the sample, other than that it is free of other Fe-containing phases. In it a single parameter, ?RT-the 'centre of gravity', or area weighted mean isomer shift at room temperature, T = 295 ± 5 K - is extracted by curve-fitting a sample's Mössbauer spectrum, and is correlated to the sample's composition or stoichiometry. We present data on high-purity magnetite and maghemite powders, and mixtures thereof, as well as comparison literature data from nanoparticulate mixtures and solid solutions, to show that a linear correlation exists between ?RT and the numerical proportion of Fe atoms in the magnetite environment: ? = Femagnetite/Fetotal = (?RT - ?o)/m, where ?o= 0.3206 ± 0.0022 mm s-1 and m = 0.2135 ± 0.0076 mm s-1. We also present equations to relate ? to the weight percentage w of magnetite in mixed phases, and the magnetite stoichiometry x = Fe2+/Fe3+ in solid solutions. The analytical method is generally applicable, but is most accurate when the absorption profiles are sharp; in some samples this may require spectra to be recorded at reduced temperatures. We consider such cases and provide equations to relate ?(T) to the corresponding ? value.

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