A wide range of transition metal oxide solid solutions have been prepared and characterised using powder X-ray diffraction (MnxCo1−xFe2O4, FexCo1−xFe2O4, NixCo1−xFe2O4, FeFexCr2−xO4, MnFexCr2−xO4, MnxFe1−xCr2O4, MnxFe1−xFe2O4, NixFe1−xFe2O4). Calibration curves have been obtained relating oxide composition to unit cell parameter or d spacing. From these curves it is possible to identify the composition of oxides formed on steel surfaces in varied industrial environments. Even when poor diffraction patterns are obtained and little sample is available, an estimate of composition can be made.