Chromium is a common contaminant of soils and aquifers and constitutes a major environmental problem. In nature, chromium usually exists in the form of two oxidation states, trivalent, Cr(III), which is relatively innocuous for biota and for the aquatic environment, and hexavalent, Cr(VI) which is toxic, carcinogenic and very soluble. Accordingly, the majority of wastewater and groundwater treatment technologies, include a stage where Cr(VI) is reduced to Cr(III), in order to remove chromium from the aqueous phase and bind the element in the form of environmentally stable solid compounds. In the absence of iron the final product is typically of the form Cr(OH)(3)center dot xH(2)O whereas in the presence of iron the precipitate is a mixed Fe(1-x)Crx(OH)(3) phase. In this study, we report on the synthesis, characterisation and stability of mixed (Fe-x,Cr1-x)(OH)(3) hydroxides as compared to the stability of Cr(OH)(3). We established that the plain Cr(III) hydroxide, abiding to the approximate molecular formula Cr(OH)(3)center dot 3H(2)O, was crystalline, highly soluble, i.e. unstable, with a tendency to transform into the stable amorphous hydroxide Cr(OH)(3)(am) phase. Mixed Fe0.75Cr0.25(OH)(3) hydroxides were found to be of the ferrihydrite structure, Fe(OH)(3), and we correlated their solubility to that of a solid solution formed by plain ferrihydrite and the amorphous Cr(III) hydroxide. Both our experimental results and thermodynamic calculations indicated that mixed Fe(III)-Cr(III) hydroxides are more effective enhancers of groundwater quality, in comparison to the plain amorphous or crystalline Cr(III) hydroxides, the latter found to have a solubility typically higher than 50 mu g/l (maximum EU permitted Cr level in drinking water), while the amorphous Cr(OH)(3)(am) phase was within the drinking water threshold in the range 5.7 < pH < 11. In comparison, the mixed Fe0.75Cr0.25(OH)(3) hydroxides studied were of extended stability in the 4.8 < pH < 13.5 range. (C) 2013 Elsevier B.V. All rights reserved.