Can the pH-dependent adsorption of phenoxyalkanoic herbicides in soils be described with a single equation?

Abstract

The six phenoxyalkanoic acid herbicides currently used in the European Union have similar molecular structures. Therefore, we assumed the soil components involved in the adsorption mechanisms of these herbicides to be identical. The values of the adsorption distribution coefficient K_d, obtained via batch experiments involving typical Polish Arenosol, Luvisol, and Chernozem profiles with a native pH of 4.2-7.7, were examined using Lasso regression, as well as adsorption on isolated fractions of humic substances, Al₂O₃, and goethite. The neutral forms of the herbicides were adsorbed on the surface of fulvic acids available to them, covering soil mesopores with a size of > 2.5 nm. The models revealed that fulvic acids had a lognormal-like distribution in soil pores. Herbicide anions were adsorbed on the pH-dependent sites of Al oxyhydroxides and on the sites created by the Al⁺³ species adsorbed on the surface of fulvic acids (both sites were active up to pH 7.5), the sites of humic acids associated with the adsorbed Al³⁺ species, sites of Fe oxyhydroxides (active at pH < 5), and, to a limited extent, sites of humins. Two models describing the adsorption of phenoxyalkanoic acid herbicides in soils were created. A simpler model was based on humic substance fractions and the variables related to the potential acidity of soils. In the more extensive model, humic substance fractions and Al and Fe oxyhydroxide contents were used as predictors, and, where necessary, the predictors were combined with the modified Henderson-Hasselbalch formula to estimate the activity ranges of pH-dependent sorption sites. The study findings revealed that fulvic and humic acids were the main adsorbents of phenoxyalkanoic herbicides in soils, indicating that transporting of the herbicides with dissolved organic matter is an important mechanism of groundwater and surface water contamination with these chemicals.