Competitive sorption of heavy metal by soils. Isotherms and fractional factorial experiments

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Competing ions strongly affect heavy metal sorption onto the solid surfaces of soil. This study evaluated competitive sorption of Cd, Cu, Ni, Pb and Zn on three soils: Calcixerollic Xerochrept, Paralithic Xerorthent and Lithic Haplumbrept. Monometal and competitive sorption isotherms were obtained at 25°C. The individual effect of ions on retention of the others was ascertained by a fractional factorial analysis design. Most of the sorption isotherms belonged to type L subtype 2 in the classification of Giles. In competitive sorption the initial linear part was shorter and the knee sharper when compared with monometal sorption isotherms. Parameters related to sorptive capacity, such as Point B, Langmuir monolayer and Freundlich distribution coefficient, were higher in monometal than in competitive sorption, and in basic soils than in acidic soil. Calcium desorbed at different points of the sorption isotherms indicated that cationic exchange with Ca was the main retention mechanism in calcareous soils. For Pb, the ratio Ca desorbed/Pb sorbed was close to one; for Cu, Ni and Zn the ratio ranged from 1.20 to 1.37, probably due to partial dissolution of calcium carbonates by hydrolytic processes during retention. On the other hand, Cd had a ratio around 0.6 reflecting another additional retention mechanism, probably surface complexation. Fractional factorial design confirmed that the presence of the cations investigated reduced the amount of the five metals retained, but the presence of Cu and Pb in the system depressed Ni, Cd and Zn sorption more than the inverse. Cation mobility was enhanced when equilibrium concentration increased and the effect was higher in Ca-saturated soils.