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This paper investigates interaction processes of the Fe3+, Cu2+, Ni2+, and Co2+ cations with humic acids isolated from brown coals of Ekibastuz basin. It was demonstrated that the sorption of heavy metal ions by humic acids (HA) depends on the concentration and nature of cations and decreases in the order of Fe3+ > Cu2+ > Ni2+ > Co2+; while increase in the concentration of humic acids (HA) results in the higher yield of ions and metals. The occurrence of ion exchange and complexation reactions in metal-humic acid systems is confirmed by the appearance of new bands and the shift of the absorption bands corresponding to stretching and deformation vibrations of carboxylate ions, C = O and OH groups. The occurrence of these processes is also evidenced by spectrophotometric data, as well as a decrease in the pH of the solution due to deprotonation of humic acids during these reactions. Thus, based on the data on the degree of sorption of metal cations by humic acids, the results of infra-red spectroscopy and spectrophotometry, it can be concluded that the Fe3+, Ni2+, Co2+, Cu2+ cations interact with HA by the ionic mechanism and by the complexation mechanism with electron-donating functional groups. Electrochemical studies of the Cu2+ – humic acid system carried out by the method of cyclic voltammetry also indicate the occurrence of the interaction of humic acid with copper cations. Modification of humic acid with copper ions shows the electrochemical activity of copper immobilized on the surface of dispersed humic acid, which is important for the implementation of electrocatalytic reactions on modified glassy carbon-humic electrodes. [ABSTRACT FROM AUTHOR]