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Data from the study of minerals of the liquidus association (olivine and spinel) from high-Mg basalts (up to 10 wt % MgO) of Menshyi Brat Volcano (Iturup Island) are reported. Based on these data, it was possible to estimate the water content and to study the evolution of volatile components in the primary basic magmas that formed the Medvezhia Caldera (Irurup Island), for the first time. It is shown that the initial water content in melts could reach 5 wt % at an oxygen fugacity corresponding to the NNO + 0.4 buffer. The further evolution of magmas included continuous degassing at a depth of ≤8 km. Hydrous fluid separated from basic magma could play a significant role in the formation of large crustal chambers of siliceous magma participation in catastrophic caldera eruptions.