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Positron annihilation characteristics as a function of composition and annealing in zinc vapour were measured and compared with photoluminescence spectra for Zn_{1-x}Mg_{x}Se mixed crystals with 0 ≤ x ≤ 0.6. The positron annihilation data show that there is a substantial number of divacancies present in the system under study. The concentration of such defects is reduced at least by the factor of two upon annealing in zinc vapour.