In this contribution, we present a study aimed at investigating the microstructural changes of ZnS single crystals and CVD (chemical vapour deposition) grown crystals after electron and proton irradiation. Positron lifetime and Doppler-broadening measurements were performed to investigate the stability of the radiation induced defects and possible clustering mechanisms during isochronal annealing. After electron as well as proton irradiation the significant changes in the annihilation characteristics are indications of radiation induced open-volume-type defects. It is found that electron and proton irradiation causes different changes in the positron annihilation characteristics. After electron irradiation a significant defect component is observed which can be attributed to the annihilation in monovacancies. During isochronal annealing agglomerations to divacancy-type defects take place. Proton irradiation reveals a significantly different defect structure. Isochronal annealing causes agglomerations to larger defect complexes. The observed annealing stages are indications of the annealing of variously sized vacancy complexes.