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Volcanic activity is one of the main sources of natural nanoparticles. It has been found earlier that the concentration of toxic metals/metalloids in nanoparticles of volcanic ash may be one or two orders of magnitude higher than in bulk sample. However, fate and behavior of toxic metals/metalloids depend on the type of their binding to nanoparticles. Hence, element species adsorbed onto pyroclastic nanoparticles and individual nanophases of metal/metalloid oxides or salts should be distinguished. For the first time, the single particle