We report on experiments which unequivocal identify the chemical nature of optical transitions related to As (2.58 eV), Ge (3.398 eV) and Se (1.49 eV) found in the photoluminescence (PL) spectra of GaN. For this purpose epitaxial GaN layers were doped by ion implantation (60 keV, 3×1012 cm−2) with the radioactive isotopes 71As and 72Se. The isotope 71As (half-life 64.28 h) decays first into 71Ge (11.43 d), which finally transmutes into stable 71Ga. The isotope 72Se decays via 72As (26 h) into stable 72Ge. These chemical transmutations were monitored with photoluminescence spectroscopy (PL). The half-lives resulting from exponential fits on our PL data are in excellent agreement with the half-lives of the isotopes. Our experiments clearly show that in each case the luminescence center involves exactly one As, Ge or Se atom. In addition to this, the results imply that no optically active GaN antisite exists.