The Enhanced Actinide Removal Plant (EARP), located on the Sellafield site, is one of the UK's most crucial radioactive effluent treatment plants. EARP removes actinides and select fission products from routine reprocessing effluents by association with a ferric iron oxyhydroxide floc, which is precipitated from acidic effluent streams by the addition of NaOH. The effluent compositions that EARP receives will change in character as the Sellafield site transitions from its current routine reprocessing operations to post-operational clean-out and accelerated decommissioning activities over the next few years. An enhanced understanding of the iron oxyhydroxide formation processes occurring in EARP would help underpin optimisation of current plant efficiency and allow better prediction of changes in efficiency as effluent composition varies. In this study, iron oxyhydroxide formation, properties and evolution with time under EARP-relevant conditions were characterized. These processes were investigated in a pure ferric nitrate system and systems with added sulfate, phosphate and boric acid using a range of techniques including SAXS, TEM and FTIR. In all the experimental systems the iron oxyhydroxide floc was composed of nanoparticulate ferrihydrite aggregated into extensive mass fractal structures. In situ SAXS experiments showed that formation proceeded via a precursor cluster pathway whereby Fe(III) clusters ~ 0.45 nm in radius form rapidly at pH 0.12 - pH 1.5 upon dropwise addition of strong NaOH to the acidic effluent simulants. Further analysis indicates these clusters are Fe13 Keggin clusters, which have previously been shown to be an important structural motif in the ferrihydrite structure. With further pH increase, cluster aggregation occurs along with precipitation of low molecular weight Fe(III) species (mostly monomers), leading to formation of ferrihydrite nanoparticles which preserve the Keggin cluster in the core. Phosphate, sulfate and boric acid exhibit varying interactions with the solid phase throughout the formation process, with both inner and outer sphere adsorption observed for different species. Ageing experiments show that the ferrihydrite floc readily undergoes transformation leading to predominantly hematite formation, except in the presence of phosphate (concentrations > 10 ppm) where transformation is entirely inhibited due to phosphate adsorption to the floc. These results progress the fundamental understanding of the iron oxyhydroxide formation and ageing processes occurring in EARP.