AbstractTrace amounts of heavy metals were preconcentrated on discs of polyurethane (PU) foam loaded with ammonium diethyldithiocarbamate (DDTC), to increase the sensitivity of XRF. Since the diameter of the cavities in the open‐cell PU foams reaches 30–300 μm, considerable heterogeneity effects might occur, which could reduce the accuracy of the method. The possible systematic error introduced by considering the sample to be homogeneous is calculated using the Berryet al.model. The calculations show that the underestimation of the absorption correction factor when considering the sample as being homogeneous is less than 2% for high‐Z elements when the sample thickness is at least 2 mm. The detection limits are also around the minima for this thi