The matrix composition and surface chemistry of high iron pyrochlore (Fe pyrochlore) grains from Niobec (St-Horone carbonatite deposit) were analyzed, in order to identify a potential relationship between Fe pyrochlore matrix composition and the related effect on cationic collector adsorption (tallow diamine). SEM–EDX analyses indicate compositional zoning in the structure Fe pyrochlores. TOF-SIMS was used to analyse the surface of different compositional zones of Fe pyrochlore, in order to identify their related effects on tallow diamine adsorption. Surface analyses of high and low iron zones of treated Fe pyrochlore show that species indicative of the collector favour the regions of low iron content The low iron areas also show a lower relative proportion of species indicative of oxidation. This study identifies the link between Fe pyrochlore compositional zoning, surface oxidation and, area selective collector loading.