Adsorption-Desorption Equilibria of Herbicides in Soil: A Thermodynamic Perspective

Abstract

Because adsorption is a major factor controlling herbicide persistence, activity, and mobility in soils, an extensive literature exists on the measurement of this process. The adsorption data are usually fitted to the Freundlich equation, but attempts to interpret this equation theoretically have had only limited success. A meaningful thermodynamic interpretation of the Freundlich equation can be developed using a proposed standard state for adsorbed herbicide, which assumes that soil organic matter forms a solid solution with the herbicide. When herbicide vapor pressures and aqueous solubilities are taken into account, the losses in free energy of different herbicides, on adsorption onto wetted soil surfaces, are shown to be similar to each other and are slightly less than the loss on absorption to the solid herbicides themselves. The Freundlich exponent is related in a simple way to the decreasing energy of available soil sites as the amount of herbicide adsorbed increases, but this change is relatively small over the range of concentrations used in adsorption experiments. Sample results are given for six triazine, three urea, and one uracil herbicides.