The amenability of limonite ore, the iron rich nickel laterite phase, was observed to be less than saprolite, the silicate rich phase, when subjected to biological leaching with heterotrophic microorganisms. To understand this difference, controlled leaching of the various nickel laterite minerals was conducted using citric acid to mimic the chemical action of the organisms and subsequent characterisation of the leached residues. The raw ore and the leached mineral residues were examined using high-resolution synchrotron based X-ray diffraction and optical microscopy. The possible contribution of electrosorption and solid porosity, was also considered. The results suggest that although electrosorption contributes to nickel and cobalt losses, it is the structural changes induced by the acid in the minerals which effects the recovery of the metals. Citric acid was found to dehydroxylate saprolite minerals resulting in an unstable nickel oxide and thus making it susceptible to acid attack. This behaviour was not observed in the limonite ore, which was found to be poorly leached by citric acid.