Although bauxites usually have a quite simple mineralogy - gibbsite (+boehmite), quartz, kaolinite, hematite, goethite, anatase (+rutile) and minor or less common phases, fine particle size, low crystallinity and variable compositions of the iron minerals might render phase quantification difficult, as well as impairing bauxite processing. A reliable and complete characterisation is therefore necessary in order to predict processing performance and ensure compliance to plant specifications. X-ray diffraction is the most important single tool for bauxite characterisation, and the constrained refinement of the Al-for-Fe substitution in goethite during one-step phase quantification by fundamental parameters Rietveld method has been successfully used. The same method was developed to analyse the coupled Al-for-Fe and OH--for-O2- substitutions in hematite. The method was tested against Mossbauer spectroscopy iron distribution on bauxite samples with a large compositional range, and on bauxite Certified Reference Materials from the main Brazilian mines, with improved results and widened range of conclusions that can be drawn related to bauxite processing. (C) 2013 Elsevier Ltd. All rights reserved.