Interaction of imidazolinone herbicides with soil humic acids. Experimental results and molecular modeling

Adsorption and desorption isotherms of the herbicides imazapyr, imazethapyr and imazaquin on a soil humic acid have been performed at pH 2.8 and 4.0 (below and above the pKa of the herbicides). At both pH, adsorption increased according to the lipophilic character of the molecules (imazapyr < imazethapyr << imazaquin). The extent of adsorption was higher at pH 2.8 than at pH 4.0 because of the partial ionization of the carboxylic groups of both herbicides and humic acids at increasing pH. Desorption of imazapyr and imazethapyr was nearly complete at pH 4 and higher than 60% at pH 2.8 while desorption of imazaquin was 45 and 8% at pH 4 and 2.8, respectively. No differences between adsorption isotherms at 10 degrees C and 25 degrees C were observed a pH 4.0 indicating that adsorption involved very weak bonds while at pH 2.8, adsorption was higher at 10 degrees C than at 25 degrees C indicating an exothermic process. The isosteric enthalpy of adsorption of each herbicide was low (about -1 kJoule mole(-1)) suggesting that low energetic bonds were involved. Adsorption on different humic acids has indicated that for each herbicide, the extent of adsorption expressed as Kd was correlated with the amount of carboxylic and aromatic groups of humic acids suggesting that hydrogen bonding and/or charge-transfer complexes formation could take place. Molecular modeling and geometry optimization of humic acid and soil organic matter (SOM) herbicide complexes were also performed. The results obtained with this theoretical approach gave a consistent chemical interpretation of the experimental results. To the best of our knowledge this is the first report to contribute to a better understanding of site-specific bonding of herbicides in SOM complexes by nanochemical modeling and distinct energy descriptors.