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Study of Interaction Between Glyphosate and Goethite Using Several Methodologies: an Environmental Perspective

Orcelli, Thiago, di Mauro, Eduardo, Urbano, Alexandre, Valezi, DanielF., da Costa, AntonioC. S., Zaia, CássiaThaïs B. V., Zaia, DimasA. M.
Water, air, and soil pollution 2018 v.229 no.5 pp. 150
Fourier transform infrared spectroscopy, adsorption, calcium chloride, desorption, electron paramagnetic resonance spectroscopy, glyphosate, goethite, groundwater, iron, models, pH, phosphates, rivers, salt content, soil, sorption isotherms, surface area
Glyphosate (N-(phosphonomethyl) glycine) is one of the most widely used herbicides in the world. Experiments using distilled water or CaCl₂ extractor resulted in as much as 60% of glyphosate being desorbed from goethite. When Mehlich 1 extractor was used, desorption could reach up to 73%. At pHs 2.0, 4.0, 6.0, and 8.0, an increase in salt content decreased the adsorption of glyphosate onto goethite. This indicates that most of the glyphosate is bound weakly to goethite through an outer-sphere complex. Thus, in soils with a high goethite content, glyphosate will contaminate groundwaters or rivers easily. FT-IR spectra showed that glyphosate interacts with goethite through the phosphate group and, at high pH, the amine group could be involved. Evidences of the interaction of the amine group of glyphosate with goethite were also obtained from the EPR spectra that showed, at high pH, a distortion in the octahedral symmetry of iron. In addition to the adsorption decrease with an increase in pH, a decrease of desorption at high pH occurs. This probably occurs because, at high pH, glyphosate interacts with goethite as a monodentate complex and through the amine group. The adsorption results fit best to a Freundlich isotherm model. This is in good agreement with the desorption results, indicating the presence of at least two adsorption sites—one for outer-sphere complexes and the other of inner-sphere complexes. The experimental results fit well with both pseudo-second-order and diffusion-limited models. The experimental results also fit well with a diffusion-limited model; however, the C value was different from zero. Therefore, the adsorption process was not controlled by diffusion only. Adsorption of glyphosate onto goethite is a complex process that could involve intra-particle diffusion. After adsorption of glyphosate onto goethite, a large decrease of pHₚzc was observed. The surface area and pore volume of goethite did not change with the adsorption of glyphosate.