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Positron-positronium annihilation spectrum were analyzed using four-component fitting procedures. It is shown that this technique can be used to investigation of nanopores transformation in humidity-sensitive MgO- Al2O3 ceramics as porosimetry method. It is established that the third component of lifetime spectra gives information about ortho-positronium decaying in nanopores with water and fourth component reflects positronium trapping in free-water volume of nanopores.