The characterisation of high-P iron ores by field emission gun electron probe microanalyser (FEGEPMA) was carried out to determine elemental associations in iron oxides sensus lato and, using this knowledge, to speculate on possible P incorporation mechanisms in goethite. Quantitative data was collected from two goethite-rich bulk ores and results showed that in both samples goethite was the main repository for phosphorus. The P-rich goethite also contained elevated levels of both aluminium and silicon.To understand the mechanism of P incorporation in goethite, high-P grains were located by coarse mapping of polished blocks with the FEG-EPMA. Analysis of element distribution maps collected on the P-rich grains showed that low-P regions within grains were typically associated with low-Al and high-Si, whereas high-P regions were associated with high-Al and low-Si. Based on follow-up quantitative analyses, a coupled substitution mechanism for phosphorus incorporation within goethite was proposed: 2Si4+ = 1P5+ + 1Al3+. Additional quantitative analyses on further examples indicated the mechanism was only valid for Si contents in goethite of <1 wt per cent.preliminary transmission electron microscope (tem) studies confirmed the presence of p, al and si in goethite.>