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The sorption of Cu2+ onto bentonite modified with Al Keggin cations and humic acid from CuCl2 solutions at pH 4.5 was studied. Modification of Na-bentonite with Al Keggin cations was found to result in an increase in the basal spacing of montmorillonite from 1.29 nm for N-form to 1.85 and 1.78 nm for HAl13 and Al13 forms respectively, in a reduction of CEC (cation exchange capacity) and in the formation of additional sites with a variable charge with pHPZC 4.2. Al13-bentonite is not affected by heat. Under the conditions of the experiments at pH of 4.5 Na-bentonite adsorbs more Cu2+ from CuCl2 solutions then Al13 forms of bentonites. The main mechanism of copper sorption on Na-bentonite is the cation exchange Cu2+&ndash, Na+. The reduction of CEC of Na-bentonite after modification with Al Keggin cations leads to a decrease in the Cu2+ sorption. pH-dependent sorption sites on Al13-bentonites have a pHPZC of 4.2 and, therefore, under conditions of the experiment have positive charge which prevents Cu2+ sorption. Na-bentonite adsorbs more humic acid solution (HA) then Al13-bentonite and the proportion of adsorbed HA remains constant over the entire concentration range. Treatment of the Al13-bentonite with HA leads to the formation of the additional sorption sites. The amount of sorbed Cu2+ and the percentage of their extraction from solutions by HAAl13-bentonite is similar to those values for Na-bentonite.