The accumulation of soil contaminants in plants can lead to health effects for humans. Leafy vegetables from some farms in the Sydney Basin contain appreciable concentrations of cadmium (Cd) derived from surface soil. Synchrotron XRF measurements of Cd and other elements in Sydney basin soils were undertaken at beam-line 2-ID-D of the Advanced Photon Source, Argonne. The sample set included a phosphate rock used in the manufacture of fertiliser, which is a likely source of Cd contamination in soils. Excellent spatial resolution (~1 μm) and sensitivity to Cd were obtained for the soils, and the Cd in the phosphate rock was readily detected and mapped. A large amount of data was obtained and various types of Cd-elemental associations were observed. The results of this work show that the synchrotron XRF technique is well-suited to examining Cd associations in soils with excellent sensitivity and spatial resolution. The combination of electron microscopy and synchrotron measurements provides valuable insights into the behaviour of contaminants in soils.