A major parameter determining the performance of X-ray emission spectrometry (XES) is the efficiency of excitation, which includes the excitation geometry. This latter factor is maximized if the X-ray excitation source is inside the specimen to be analyzed. The objective of this study is to assess XES with in-situ X-ray excitation from radioactive implants: mixing the sample in solution with a radiosotope, or bombardment of a solid specimen with a radioactive ion beam.