Abstract

The physicochemical dynamics of a pesticide-sediment-water system were studied utilizing a one-dimensional numerical model of diffusion under saturated conditions, with nonlinear Freundlich/Langmuir adsorption-desorption. Specifically, the model was formulated to assess the pollution potential of pesticides to aquatic systems, based upon their ability to migrate within the aquatic environment.

Initial physical and chemical characterization of eight freshwater sediments, and adsorption studies using two chemically dissimilar herbicides—bromacil and diquat—revealed insightful positive relationships between adsorption coefficients and sediment properties. Bromacil showed a high positive correlation between the Freundlich sorption partition coefficient and the organic carbon content. Diquat adsorption, as characterized by a Langmuir-type adsorption, showed a high positive correlation between the Langmuir affinity constant and the surface area, while the Langmuir adsorption maxima correlated highly with the cation exchange capacity of sediments treated for the removal of organic matter. Apparent heats of adsorption for bromacil at 5° and 25°C were low, indicating a predominantly physical type of adsorption. Temperature change was found to have little or no effect upon the adsorption of diquat over the range of observed temperatures, 5° and 25°C. Rates of adsorption for both bromacil and diquat were very rapid, especially on sediments with small organic matter fractions. In general, diquat took slightly longer than bromacil to attain equilibrium. The slower adsorption rate of diquat on high-organic-matter sediments confirms previous findings indicating a possible redistribution of diquat from adsorption sites on the organic fraction to adsorption sites on the clay surface. Varying the initial solution concentration of either bromacil or diquat did not significantly affect the reaction rates. Desorption studies for bromacil and diquat showed that for each sediment, a unique linear relationship existed between the adsorbate concentration at which desorption began and the slope of the desorption isotherm.