Sample-size reduction including homogenization is often required to obtain a test portion for element compositional analysis. Analyses of replicate test portions may provide insight into the sampling constant, and often much larger quantities are needed to limit the contribution of sampling error. In addition, it cannot be demonstrated that the finally obtained test portion is truly representative of the originally collected material. Nuclear analytical techniques such as neutron and photon activation analysis and (neutron-induced) prompt gamma activation analyses can now be used to study and overcome these analytical problems. These techniques are capable of obtaining multi-element measurements from irregularly shaped objects with masses ranging from multiple grams to multiple kilograms. Prompt gamma analysis can be combined with neutron tomography, resulting in position-sensitive information. The analysis of large samples provides unprecedented complementary opportunities for the mineral and geosciences. It enables the experimental assessment of the representativeness of test portions of the originally collected material, as well as the analysis of samples that are not allowed to be sub-sampled or dissolved, the analysis of materials that are difficult to be homogenized at large, and studies on the location of inhomogeneities. Examples of such applications of large-sample analyses are described herein.