Effect of pedogenic iron-oxyhydroxide removal on the metal sorption by soil clay minerals

The close association of Fe-oxyhydroxides and clay minerals might influence the sorption properties of these components. We aimed to study the effect of removing the pedogenic Fe-oxyhydroxides on the sorption of Cd, Cu, Pb, and Zn by the clay mineral particles in soils with contrasting pH. Competitive batch sorption experiments before and after Fe-oxyhydroxide extraction in soils were carried out together with the direct analysis of the metal sorption on individual particles of ferrihydrite, smectite, and illite/smectite by TEM. Ferrihydrite was a more effective metal sorbent than clay minerals, although its removal resulted in decreased sorption only for Cd, Cu, and Zn. Ferrhydrite coating blocked metals’ access for certain sorption sites on clay surfaces, which were only accessible for Pb as the most efficient competitor after removing the coating. This observation was the most remarkable for the smectite particles in the alkaline soil. Mineral surfaces sorbed higher Cu than Pb concentrations and higher Zn than Cd concentrations despite the former metals’ lower bulk sorption. Thus, organic surfaces and precipitation contributed to Pb and Cd’s retention to a greater extent than for Cu and Zn. The structural Fe of smectite also promoted the metal sorption in both soils. Removal of iron-oxyhydroxide coatings from the soil affects metal sorption selectively. Direct study of metal sorption on individual soil particles enables us to gain a more in-depth insight into soil minerals’ role in this process.