An apparatus and method are disclosed for localizing an element of interest in a sample by comparing XRF spectra acquired from at least two distinct but overlapping inspection volumes. The inspection volumes are varied by changing the geometry of the exciting x-ray and/or fluoresced x-ray beam(s), which may be accomplished by repositioning multi-apertured collimators. Comparison of the XRF spectra acquired from different inspection volumes provides an indication as to whether the element of interest (e.g., lead) is present in a coating layer, in the underlying bulk material, or in both.