Some aspects of the adsorption of glyphosate and its degradation products on montmorillonite

Abstract

The most worldwide used herbicide is glyphosate, phosphonomethylglycine (PMG). Consequently, a significant amount of PMG, its metabolites (sarcosine, SAR, and aminomethylphosphonic acid, AMPA) and the degradation product, methylphosphonic acid (MPA), reaches the soil, which acts as final sink. Because clays are one of the most reactive components of soils, expansive clays such as montmorillonite (Mt) are used to retain agriculture contaminants with some success. In this work, as a preliminary step for the evaluation of the risk that PMG, SAR, AMPA, and MPA occurrence could have on the environment, their adsorption on Mt surface was performed. The adsorption process was analyzed at constant adsorbate concentrations and two pH values to take into account the different protonation states of the amino group. DTA, XRD, zeta potential measurements, and XPS were used to identify the interactions or association mechanisms with the clay surface, the entry of adsorbates into the Mt interlayer, and electric charge changes on the Mt surface, and evaluate the acid-base surface complex constants, respectively. The interlayer thickness in acid media indicated that adsorbates are able to enter the interlayer in planar form. Besides, for the Mt-PMG sample, some PMG molecules could be also inserted as a bilayer or with a tilt angle of 52.4° in the interlayer. However, in alkaline media, the interlayer thickness indicated that the adsorbate arrangement differed from that of acidic media where PMG and MPA could have more than one orientation. The surface complex deprotonation constants were determined for the =NH+2 ⇆ =NH+H+ process, being 3.0, 5.0, and 7.3 for PMG, AMPA, and SAR, respectively.