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Ion charge state distributions due to vacancy cascades following K-, L 1 -, L 2 -and L 3 -shell ionization are calculated using a Monte Carlo technique. Probabilities P (q) that the de-excited ions become q-fold ionized after a single primary ionization are given as a function of the atomic number in the region Z = 10-60. The calculations are accomplished by tracing successive radiative and non-radiative transitions and electron shake-off as an additional effect. Thereby, radiative and non-radiative transition rates and shake-off probabilities have been calculated from relativistic wavefunctions. † Permanent address: