Data analysis methods for iron X-ray Absorption Spectroscopy (XAS) can provide extensive information about the oxidation state and co-ordination of an Fe-species. However, the extent to which techniques developed using a single-phase iron sample may be applied to complex, mixed-phase samples formed under real-world conditions is not clear. This work uses a combination of pre-edge fitting and linear combination analysis (LCA) to characterise the near edge region of the X-ray absorption spectrum (XANES) for a set of archaeological iron corrosion samples from a collection of cast iron cannon shot excavated from the Mary Rose shipwreck and compares the data with phase compositions determined by Synchrotron X-ray Powder Diffraction (SXPD). Archaeological powder and cross-section samples were compared to a library of iron standards and diffraction data. The XANES are consistent with previous observations that generation of the chlorinated phase akaganeite, β-FeO(OH,Cl), occurs in those samples which have been removed form passive storage and subjected to active conservation. However, the results show that if any metallic species is present in the sample, the contribution from Fe(0) to the spectral region containing a pre-edge for oxidised iron - Fe(II) and Fe(III) - causes the analysis to be less effective and the conclusions unreliable. Consequently, while the pre-edge fitting methodology may be applied to a mixture of iron oxides or oxyhydroxides, the procedure is inappropriate for a mixed metal-oxide sample without the application of a complimentary technique, such as SXPD
