The crystallization kinetics of goethite were studied colorimetrically under highly alkaline conditions (pH 10.1–12.2) at temperatures from 40° to 85°C. Color changes during crystallization from fresh precipitates, plotted on a*-b* colorimetric diagrams, were used to discriminate between pure goethite and mixtures of goethite and hematite. Only the b* value increased as goethite crystallization proceeded, and even a minor increase in the a* value revealed the existence of hematite. The rate of goethite crystallization, estimated from the b* value, could be modeled by a pseudo-first-order rate law. This rate depended both on pH and on temperature. Apparent activation energies for the reactions of 56.1 kJ/mol at pH 11.7 and 48.2 kJ/mol at pH 12.2 were estimated from Arrhenius plots.

The effects of neodymium (Nd) on the transformation of ferrihydrite to iron oxides was studied. The possible isomorphous substitution of Nd3+ for Fe3+ in iron oxides was examined also. Nd was used as an inactive substitute of trivalent radioactive actinide elements. Hydrolysis of ferric nitrate solution containing 0–30 mole % of Nd formed Nd, Fe-rich ferrihydrite as initial precipitates, which were poorly crystalline. Aging of the Nd-containing ferrihydrite in 0.3 M OH− at 40°C and at pH 9.2 at 70°C formed Nd-free goethite and Nd-substituted hematite. The abundance of these crystalline phases was related to Nd in the parent solutions. Phase abundance, unit-cell parameters, and peak width were estimated by use of the Rietveld method.

The chemical forms of iron minerals and uranyl species have been examined non-destructively by visible microspectroscopy and electron microprobe analysis in order to obtain a better understanding of uranium redistribution and fixation mechanisms. The uranyl species are associated with sub-micron sized iron minerals, such as hematite (Fe2O3), goethite (FeOOH), and ferrihydrite (Fe4-5(OH,O)12). Additionally, some uranium is fixed to goethite in weathered chlorite grains. Sub-micron sized saleeite, Mg(UO2)2(PO4)2. 1OH2O, is the most probable uranyl phase associated with the iron minerals. This suggests that the uranium fixation in the vicinity of the Koongarra uranium ore deposits is the result of the coprecipitation and sorption of microcrystals of saleeite on to the iron minerals released during weathering of chlorite.