Sulfate adsorption by variable charge soils: Effect of low-molecular-weight organic acids

Abstract

Sulfate (SO₄ ^2–) movement and transport in soils has received considerable attention in recent years. In most soils, SO₄ ^2– coexists with a variety of natural organic compounds, especially organic acids. Studies were conducted to assess the effect of low-molecular-weight organic acids (eight aliphatic and five aromatic acids) on SO₄ ^2– adsorption by variable charge soils from Chile and Costa Rica. The effects of type of organic acid, pH, type of soil, and organic acid concentration were investigated. In one experiment, a 1.0 g soil sample was equilibrated with 25 ml 0, 0.5, 1.0, 2.0, 4.0, or 6.0 mM K₂SO₄ in 1 mM NaCl in the presence or absence of 5 mM citric acid. In the second set of experiments, the adsorption of 2 mM SO₄ ^2– in soils at pH 4 or pH 5 in the presence or absence of one of 13 organic acids at a concentration of 2 mM or 5 mM was studied. Results showed that citric acid significantly decreased SO₄ ^2– adsorption by the two soils. Sulfate adsorption decreased with increasing pH of the equilibrium solution. Aliphatic acids, with the exception of cis-aconitic acid, decreased the amount of SO₄ ^2– adsorbed by the two soils, with oxalic, tartaric, and citric acid showing the greatest effect. The differences in pH values of the equilibrium solutions in the presence and absence of organic acids were significantly, but negatively, correlated with the amount of SO₄ ^2– adsorbed, suggesting chemisorption of SO₄ ^2– and the release of hydroxide ions. The ionization fraction values of the organic acids at the equilibrium pH were correlated with the amounts of SO₄ ^2– adsorbed, suggesting that the protonation of surface hydroxyl groups of the mineral phase increased as the strength of the ionization of the acid increased, thus creating more positively charged surfaces.