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The binding of Cd(II) to soil humic acid (HA) at pH 6.5 and in 0.1 mol/L KNO3 ionic medium, was studied by potentiometric titration with a cadmium ion selective electrode. The influence of carboxyl groups in cation-humic interactions was investigated by selective blocking of humic acid carboxyl groups with thionyl chloride and methanol. Infrared spectroscopic analysis confirmed that esterification took place. Differences between underivatized and derivatized HA complexation properties are ascribed to carboxyl groups. The Scatchard plots and incremental formation constants were used to obtain values for Cd-binding constants, for both HAs. The derivatization decreased the number of HA complexing sites by approximately 60 %, which correlates with acid-base properties of both HAs, studied by barium hydroxide and calcium acetate exchange methods. The stability constants for binding at the strongest sites (logK INT ) was larger for underivatized HA (5.40) than for derivatized HA (4.92), indicating greater stability in the case when carboxyl groups are involved in complexation reaction.

Binding of cadmium to soil humic acid as a function of carboxyl group content