In this study we aim to identify elements that can act as geochemical indicators within the Yellowknife greenstone belt that allow the discrimination of mineralized structures. The ability of pXRF to provide a fast and accurate assessment of compositions depends on particle sizes and chemical homogeneities within various lithologies. Therefore, we have tested the precision and accuracy of pXRF in six drill cores with heterogeneous mineralogy, lithology and grain sizes from various locations across the Yellowknife Greenstone Belt against standard assay data and ICP data from Gold Terra. The pXRF analysis picks up distinct geochemical trends approaching mineralized structures and surrounding alteration/shear zones, however the trends vary by location and host rock lithology. Mineralogical variability as a function of distance from gold-bearing structures has been determined to assess what minerals control the geochemical trends detected.