The GEANT4 Monte Carlo code has been used to simulate gamma-ray spectra of natural radionuclides collected by a NaI scintillation detector immersed in seawater. The gamma-rays emitted from the decay of (40)K, and the series of (232)Th and (238)U, were used to describe the radioactive water source around the NaI crystal. The simulated gamma-ray spectra were compared with real data recorded in situ by a newly constructed NaI spectrometer and were found to be in good agreement. The NaI spectrometer was calibrated in the laboratory in a water tank, before its deployment in seawater. Activity concentrations were deduced from the gamma-ray spectra and discussed in comparison with results from the literature.