Zinc Sorption by Manganese‐Oxide‐Coated Sand as a Function of pH

Abstract

Abstract Manganese oxides in soils may be sites for sorption of heavy‐metal cations, but the roles of pH‐dependent charge and oxide mineralogy remain unclear as controls on exchangeability of the metals. A model soil‐oxide system tested the effect of pH on the amount and form of Zn retained in exchangeable or nonexchangeable fractions on birnessite‐hausmannite‐coated sand or pyrolusite‐coated sand. Two Zn treatments, 250 and 2500 µmol/kg sand, were used to determine the effect of Zn concentration on the form of Zn retained. Surface charge for the birnessite‐hausmannite‐coated sand and pyrolusite‐coated sand increased across the pH range from 4 to 7.6, but surface charge was found to be a poor predictor of the amount and form of Zn retained even though the oxides increased Zn sorption by the sand. The distribution between the exchangeable and nonexchangeable Zn fractions changed from predominantly exchangeable to predominantly nonexchangeable Zn due to the oxide coatings and higher pHs. The difference in the exchangeable and nonexchangeable Zn retention by the two sands was attributed to mineralogical constraints on the type of surface functional groups. The mechanisms proposed to account for the nonexchangeable retention of Zn on both oxide‐coated sand surfaces were hydrolysis of the Zn followed by chemisorption to the oxide surface.