A set of early chemical reactions induced in frozen medium around decayed 57 Co or 119m Sn nuclei by emitted Auger electrons is suggested. The mechanism predicts a correlation between formation probabilities of final products, namely Fe 2+ -Fe 3+ or Sn 2+ -Sn 4+ ions, positronium atom and molecular hydrogen formed in similar medium after its irradiation by fast positrons and electrons. This correlation indicates a similarity of chemical processes occurring in nanovolumes around Mö ssbauer 57 Fe-and 119 Sn-nuclei after radioactive decay as well as in tracks produced by fast positrons and electrons. The important role of quasi-free electrons is revealed.Key words reaction of electrons . comparative study . emission Mö ssbauer spectroscopy . positron spectroscopy . radiolysis For application of the emission Mö ssbauer spectroscopy, a small amount of special isotopes ( 57 Co, 119m Sn) are added into investigated solid state system. A common property of these isotopes consists in production of Auger ionization of the daughter atoms ( 57 Fe, 119 Sn), caused by electron capture or converted isomeric transition. These processes precede emission of the Mö ssbauer g-quantum by Mö ssbauer 57 Fe or 119 Sn, which carries physico-chemical information about the daughter atoms and their environment. Auger ionization converts the daughter atom into multi-charge ion (electric charge of 57 Fe ion could reach +8) and is accompanied by emission of a large number of Auger electrons with total energy about several keV and average energy of the electron above 10 2 eV. Together with the X-rays, Auger electrons Hyperfine Interact (2005) 166:437-442